CN104726140B - A kind of iron oxide sulfur method and equipment - Google Patents
A kind of iron oxide sulfur method and equipment Download PDFInfo
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- CN104726140B CN104726140B CN201510137383.1A CN201510137383A CN104726140B CN 104726140 B CN104726140 B CN 104726140B CN 201510137383 A CN201510137383 A CN 201510137383A CN 104726140 B CN104726140 B CN 104726140B
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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
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/105—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur
- C10K1/106—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur containing Fe compounds
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Abstract
The present invention provides a kind of iron oxide sulfur method and equipment, sulfur method to include：Desulfurizing agent and strong acid weak base salting liquid are mixed to form complex iron oxide desulfurizing agent, carry out desulfurization is inversely contacted with coke-stove gas；Wherein, desulfurizing agent is one or both of brown iron oxide and hydrated ferric oxide desulfurizing agent.Desulphurization plant includes：Wet desulfuration tower；The wet desulfuration tower includes tower body, the liquid outlet for going out tower into the first air inlet of tower and the complex iron oxide desulfurizing agent being useful for after desulfurization for coke-stove gas is provided with the downside of tower body side wall, the first gas outlet for going out tower for coke-stove gas is provided with the top of tower body, liquid distribution trough and lower liquid distribution trough are provided with tower body, it is separately provided for the packing layer of increase Gas-liquid interfacial area immediately below the underface of upper liquid distribution trough and the lower liquid distribution trough, the top in tower body is provided with reverse V-shaped fold-type porous plate.Sulfur method and equipment desulfurization effect are good, and desulfurizer activity is high.
Description
Technical field
The present invention relates to coke-stove gas, natural gas, coal gas desulfuration field, in particular to iron oxide sulfur method
And equipment.
Background technology
Coke-stove gas is without using being vented, not only causing the wasting of resources, but also huge pollution is caused to environment.By coke-oven coal
It is both industrial chemicals that gas, which is changed into, and the methanol of clean fuel is as hot spot in recent years.In ripe methanol-fueled CLC scheme
In, economy is best to be included coking (oven gas) connection alcohol, chemical fertilizer (synthesis ammonia) joins alcohol and utilizes sulphur coal multiple-supplying production first
Alcohol.With using coal compared with raw material, coke-stove gas as synthesizing methanol, synthesis ammonia and hydrogen manufacturing raw material, have plant investment it is few, money
The characteristics of low with cost of material, is enriched in source, and economic advantages are obvious.The resource of coke-stove gas maximally utilizes, and meets China's construction section
About type society, environmental protection, circular economy and resource, environment and socio-intangible asset and the state basic policy of sustainable development, and coal Ji Jia
Another way of realization of alcohol and coal base synthesis ammonia.
Containing impurity such as Determination of Trace Sulfur, alkene, oxygen, tar, naphthalene, hydrogen cyanide, ammonia and benzene in coke-stove gas.Coke-stove gas conduct
Industrial chemicals causes catalyst member in use, these impurity can cause to poison to the catalyst in follow-up chemical engineering process
Or complete deactivation.Especially modern efficient synthetic catalyst, it is desirable to which sulfur content is less than 0.1 × 10 in synthesis gas-6, and coke-stove gas
Also the content of impurities such as alkene are required to be less than 50 × 10 as far as possible before into steam reforming catalysts-6.Therefore, either as work
Industry raw material or domestic fuel, the sulphur impurity in efficient removal coke-stove gas, be coke-stove gas recycling key, and
The hot spot of recent research.
Nowadays, the sulfur method of coke-stove gas is mainly the following method：
1st, iron oxide process
Iron oxide process sulfur removal technology is a kind of traditional sulfur method of classics, can by the sulfur content in coke-stove gas by
2000mg/Nm3It is reduced to 200mg/Nm3Below (in terms of S), desulphurization mechanism H2Liquid films of the S in iron oxide hydrate particle surface
In be dissociated into H+、SH-And S2-, then with the Lattice Oxygen (OH in hydrated ferric oxide-、O2-) interaction generation Fe2S3·H2O.Its
Reaction equation is：Fe2O3·H2O+3H2S→Fe2S3·H2O+3H2O iron oxide should be in alkalescence, room temperature and the condition for keeping hydrated form
Lower operation.The regenerative response formula of normal temperature iron oxide is：Fe2S3·H2O+3/2O2→Fe2O3·H2O+3S
Theoretical sulfur capacity by analyzing iron oxide pointed out when the 50-80% of iron oxide is changed into sulfide, just should be into
The regenerative response of row desulfurizing agent.But the content of strictly control oxygen is needed in actual operation, avoid in desulfurizing agent Surface Creation sulphur
After simple substance, H2S diffusion hindereds, and ferric oxide desulfurizer regeneration is an exothermic process, and if regeneration is too fast, heat release is violent,
The easy catching fire of desulfurizing agent causes fire, has security risk.
2nd, activated carbon method
Activated carbon dry desulfurizing process can be divided into absorption method, catalysis method and oxidizing process according to desulphurization mechanism.
Absorption method active carbon desulfurization can have very big specific surface area according to activated carbon, and it selects characterization of adsorption to carry out Jiao
The removing of sulphur impurity in producer gas.This method is maximally efficient to removing thiophene, but since the Sulfur capacity of this kind of activated carbon is too small so that
The removing of thiophene never obtains effective approach in industrialization.
Catalysis method active carbon desulfurization is activated carbon after dipping copper, iron isoreactivity metal, and coke-stove gas has by desulfurizing agent
Machine sulphur is catalytically conveted to hydrogen sulfide, then the method for being tightly held by activated carbon or being removed to follow-up fine de-sulfur workshop section.Conventional carbon
Desulfurization is low with reaction rate due to adsorbing, and Sulfur capacity is relatively low, it is difficult to reaches industrially desulfurized requirement.
Oxidizing process active carbon desulfurization is most common sulfur method, oxygen exist and alkaline condition under, H2S is by O2It is oxidized to
Elemental sulfur, its reaction equation are：2H2S+O2→2H2O+2S, COS and O in organic sulfur2Reaction, is converted into elemental sulfur, reaction equation
For：2COS+O2→2CO2+ 2S, continuous with reaction carry out, and the elemental sulfur of production is gradually adsorbed in the micropore in activated carbon,
This requires activated carbon possesses certain micropore quantity, its aperture also there are certain requirements.Although three of the above activated carbon method should
With also than wide, but it is changed into sweetening process and the micro- of activated carbon surface and blocking activities charcoal is easily deposited in after sulphur simple substance
Duct, and activated carbon method Sulfur capacity itself is low, and reaction rate is not also high, it is impossible to meets the requirement of desulfurization rapidly.
In view of this, it is special to propose the present invention.
The content of the invention
It is an object of the invention to provide a kind of method of iron oxide desulfurization, the iron oxide sulfur method has operation
Simply, the advantages that easily operated, desulfurization effect is good, raising desulfurizer activity.
It is another object of the present invention to provide a kind of iron oxide desulphurization plant, the iron oxide desulphurization plant has
It is simple in structure, the advantages that floor space is small, cost is low and desulfurization effect is good.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
An embodiment of the present invention provides a kind of iron oxide sulfur method, include the following steps：
Desulfurizing agent and strong acid weak base salting liquid are mixed to form complex iron oxide desulfurizing agent, inversely contacted with coke-stove gas into
Row desulfurization；Wherein, the desulfurizing agent is one or both of brown iron oxide and hydrated ferric oxide desulfurizing agent.
Further, the molar ratio of the cation in the iron ion and strong acid weak base salt in the desulfurizing agent is 1-100:1.
In the strong acid weak base salt or acid salt, cation NH4 +、Mg2+、Al3+、Fe3+、Zn2+Middle one or more,
Anion is SO4 2-、Cl-One or both of.
Further, after the complex iron oxide desulfurizing agent is inversely contacted progress desulfurization with coke-stove gas, the side
Method further includes following steps：It will be regenerated for the complex iron oxide desulfurizing agent after desulfurization, and by the coke-stove gas after desulfurization
Further desulfurization is carried out using dry desulfurization；
Preferably, the dry desulfurization is the one of which in activated carbon method and iron oxide process.
Further, the regeneration method includes：By for being passed through air in the complex iron oxide desulfurizing agent after desulfurization
Regenerated.
The embodiment of the present invention additionally provides a kind of iron oxide desulphurization plant, including：Wet desulfuration tower；The wet desulfuration tower
Including tower body, it is provided with the downside of the tower body side wall for coke-stove gas into the first air inlet of tower and after being useful for desulfurization
Complex iron oxide desulfurizing agent goes out the liquid outlet of tower, and the first outlet for going out tower for coke-stove gas is provided with the top of the tower body
Mouthful, be provided with liquid distribution trough and lower liquid distribution trough in the tower body, the underface of the upper liquid distribution trough with it is described
The packing layer of increase Gas-liquid interfacial area is separately provided for immediately below lower liquid distribution trough, the top in the tower body
It is provided with reverse V-shaped fold-type porous plate.
Further, regenerating tank, air pump, the first pipeline, second pipe, the 3rd pipeline and air pipeline are further included；
Inlet, air intlet, purified liquor outlet and turbid outlet are respectively arranged with the side wall of the regenerating tank, the regenerating tank
Tank bottom is additionally provided with raffinate outlet；
The inlet is connected by the first pipeline with the liquid outlet, the purified liquor outlet by second pipe with it is described
The import connection of upper liquid distribution trough, the turbid outlet are connected by the 3rd pipeline with the import of the lower liquid distribution trough,
The gaseous phase outlet of the air pump is connected by pipeline with the air intlet.
Further, dry desulfurizing tower and the 4th pipeline are further included；The side wall of the dry desulfurizing tower is provided with second
Air inlet and the second gas outlet for going out tower for reaching the coke-stove gas of desulfurization standard, wherein, second air inlet passes through
4th pipeline is connected with first gas outlet.
Further, humidistat is further included, the humidistat is arranged on the 4th pipeline.
Further, clear liquid pump and turbid pump are further included, the clear liquid pump is arranged on the second pipe, described turbid
Liquid pump is arranged on the 3rd pipeline.
Compared with prior art, beneficial effects of the present invention are：
(1) the iron oxide sulfur method of the embodiment of the present invention is easy to operate, and raw material sources are easy to get extensively, can not only reduce
The usage amount of hydrability iron oxide and using on the premise of equal ferric oxide desulfurizer dosage, moreover it is possible to lift desulfurization effect
Fruit；
(2) the iron oxide desulphurization plant of the embodiment of the present invention is compact-sized, and floor space is small, and desulfurization effect is good, can
By the sulfur content in coke-stove gas by original 2000mg/Nm3It is reduced to 20mg/Nm3Below.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is the structure chart of the iron oxide desulphurization plant of an embodiment of the present invention；
Reference numeral：
1- wet desulfuration towers；The first air inlets of 2-；3- liquid outlets；
The first gas outlets of 4-；5- fold-type porous plates；6- regenerating tanks；
7- air pumps；8- dry desulfurizing towers；9- humidistats；
10- clear liquid pumps；11- turbids pump；12- filters；
13- heaters.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is
The conventional products that can be obtained by commercially available purchase.
An embodiment of the present invention provides a kind of iron oxide sulfur method, include the following steps：By desulfurizing agent and strong acid weak base
Salting liquid is mixed to form complex iron oxide desulfurizing agent, and carry out desulfurization is inversely contacted with coke-stove gas；Wherein, the desulfurizing agent is oxygen
Change one or both of iron powder and hydrated ferric oxide desulfurizing agent.
Iron oxide sulfur method provided in an embodiment of the present invention, by by the brown iron oxide of commercially available acquisition, hydrated ferric oxide
Desulfurizing agent and strong acid weak base salting liquid cooperatively form mixed solution state, by of the prior art using iron oxide dry desulfurization
Method changes over the method using iron oxide wet desulphurization, and strong acid weak base salt plays catalyst and provides the work of system environment
With in view of the ion-reaction equation that ferric oxide desulfurizer carries out system generation in sweetening process is mainly as follows：
2Fe3++H2S=2Fe2++2H++S
6H++Fe2O3=2Fe3++3H2O
By adding strong acid weak base salt, it is possible to reduce the usage amount of hydrability iron oxide so that iron ion is with three valence states
Formed and existed, preferably remove sulphur, acidity is not easy too strong, and pH value is between 4-7, if using strong acid due to acid mistake
By force, hydrogen sulfide is more difficult under conditions of PH is less than 4 is dissolved in solution, is so unfavorable for removing.In addition to iron oxide type
Requirement it is also not high, reduce cost payout, while the catalytic activity of desulfurizing agent can also be improved, increase the H of desulfurizing agent2The suction of S
Yield, improves the Sulfur capacity of desulfurizing agent.In strong acid weak base salt, cation NH4 +、Mg2+、Al3+、Fe3+、Zn2+In one kind or several
Kind, anion SO4 2-、Cl-One or both of, for example can be NH4Cl、AlCl3And FeCl3Middle one or more,
As long as weak acid environment can be provided.
Further, the molar ratio of cation is 1-100 in the iron ion and strong acid weak base salt in desulfurizing agent:1.
In the present invention, after the complex iron oxide desulfurizing agent is inversely contacted progress desulfurization with coke-stove gas, the side
Method further includes following steps：It will be regenerated for the complex iron oxide desulfurizing agent after desulfurization, and by the coke-stove gas after desulfurization
Further desulfurization is carried out using dry desulfurization；The dry desulfurization is preferably wherein one in activated carbon method and iron oxide process
Kind.
In regenerative process, the ion-reaction equation mainly occurred is as follows：
12Fe2++3O2+8H2O=4Fe (OH)3+8Fe3+
By more than regenerative response equation it can also be seen that, due to there is Fe in the moisture film solution of formation3+, so formed
S formed precipitation and Fe3+After separating, Fe2+Fe can occur rapidly with oxygen3+, have the advantages that regeneration is rapid, and will
Dry method, which changes over wet method, can make it that subsequent oxidation iron desulfurizer regeneration is easy, and the regeneration that original gas phase is contacted changes
Into the mode of liquid phase, since regeneration is an exothermic process, the easy catching fire of the too fast desulfurizing agent of heat release causes fire, has
Security risk, the possibility of security risk generation is reduced by varying phase.In addition, regeneration method is specially：It will be used for
Air is passed through in complex iron oxide desulfurizing agent after desulfurization to be regenerated.It is this to be carried out by way of being passed through air into solution
Regeneration had not only facilitated but also safety.
After wet desulphurization has been carried out, the substantial amounts of sulphur in coke-stove gas is removed, but in order to enable its desulfurization
Completely, the wet desulphurization of the present invention and the dry desulfurization of the prior art can also be coordinated, frequently with dry desulfurization have
One of which in activated carbon method and iron oxide process.Sulfur removal rate after being used in combination by two methods can be by coke-oven coal
Sulfur content in gas is by original 2000mg/Nm3It is reduced to 20mg/Nm3Below (in terms of S), desulfurization effect is significantly larger than existing skill
Sulfur method in art.
An embodiment of the present invention provides a kind of iron oxide desulphurization plant, as shown in Figure 1, including：Wet desulfuration tower 1；It is described
Wet desulfuration tower 1 includes tower body, be provided with the downside of the tower body side wall for coke-stove gas into tower the first air inlet 2 with having
Go out the liquid outlet 3 of tower for the complex iron oxide desulfurizing agent after desulfurization, be provided with to go out for coke-stove gas at the top of the tower body
First gas outlet 4 of tower, is provided with liquid distribution trough and lower liquid distribution trough in the tower body, the upper liquid distribution trough
Underface and the packing layer that increase Gas-liquid interfacial area is separately provided for immediately below the lower liquid distribution trough, it is described
Top in tower body is provided with reverse V-shaped fold-type porous plate.The wet desulfuration tower can be very good to realize using wet desulphurization
Mode carries out desulfurization, and coke-stove gas enters from the side wall of wet desulfuration tower close to the place of downside, complex iron oxide desulfurizing agent from
The up or down liquid distribution trough of wet desulfuration tower enters, both realize coke oven gas desulfurization at reverse contact.And the invention
Property the top in tower body be provided with reverse V-shaped fold-type porous plate 5, the reason is that, wet desulfuration tower gas by spray
After absorption, substantial amounts of fine droplet is entrained with upward motion process, and also contains a certain amount of hydrogen sulfide in gas
And drop has certain corrosivity, this can greatly promote the requirement of the material of follow-up equipment, so that equipment cost is improved,
And meeting heavy corrosion lower procedure equipment, reduce service life of equipment.Fold-type porous plate can be blocked the drop in gas
Cut, drop is formed liquid film on the surface of fold-type porous plate, the hypomere of wet desulfuration tower is returned to using gravity stream, in order to enable
Fold-type porous plate can preferably intercept drop, it is the fold-type porous plate of multilayer.
In addition, two sections packing layer is used to increase the area that gas-liquid is in contact, strengthen desulfuration efficiency, general filler can be with
Select ceramic ring, Raschig ring etc..The density of packing layer is that upper strata is more than lower floor.
Further, iron oxide desulphurization plant further includes regenerating tank 6, air pump 7, the first pipeline, second pipe, the 3rd pipe
Road and air pipeline；Inlet, air intlet, purified liquor outlet and turbid is respectively arranged with the side wall of the regenerating tank to go out
Mouthful, the tank bottom of the regenerating tank is additionally provided with raffinate outlet；The inlet is connected by the first pipeline with the liquid outlet, institute
Purified liquor outlet is stated to be connected with the import of the upper liquid distribution trough by second pipe, turbid outlet by the 3rd pipeline with
The import connection of the lower liquid distribution trough, the gaseous phase outlet of the air pump are connected by pipeline with the air intlet.It is logical
Cross air pump to be pumped into air inside regenerating tank from outside environment, the complex iron oxide desulfurizing agent regenerated in regenerating tank is divided into clearly
Liquid and turbid, back to carrying out recycling desulfurization in wet desulfuration tower.In the clear liquid that the upper liquid distribution trough on upper strata comes out
Fe elements it is more exist in the form of trivalent ion, since clear liquid pH value is higher, lower floor can not be removed to complete H2S absorbs,
The salt added, which can hydrolyze, absorbs H2S, generates S2-, a small amount of Fe for containing3+Can also a small amount of desulfurization.Fe(OH)3As work
Property component also assists in, and the turbid in the lower liquid distribution trough of lower floor contains Fe (OH) more3And Fe2O3, since pH value is smaller, Fe3+
Remove H2S, generation acid, and acid can be with Fe2O3Neutralization reaction.If air pump break down, desulfurization operations also can normally into
OK.
The material for exporting out from the raffinate of the tank bottom of regenerating tank then cannot directly return to wet desulfuration tower, regenerate pot bottom
The raffinate component given off is drusen, strong acid weak base salting liquid, Fe3+、Fe2S3、Fe2+.The processing method of its raffinate includes：
Raffinate mainly contains strong acid weak base salt, Fe after the filtering of filter 123+Liquid be back to regenerating tank and recycle；Solid is then
It is heating furnace or steam-heated mode by heater 13, makes sulfur granules and Fe2S3The FeS separation formed after decomposition, simple substance
Sulfur releasing, sulphur can be used as commodity can direct export trade, and FeS is then back to regenerating tank and continues to regenerate.Or directly burn
The mode of burning, generates Fe2O3And SO2, SO2It can be absorbed with method for distinguishing.
Further, iron oxide desulphurization plant further includes 8 and the 4th pipeline of dry desulfurizing tower；The dry desulfurizing tower
Side wall is provided with the second air inlet and the second gas outlet, and second air inlet passes through the 4th pipeline and first gas outlet
Connection.Substantial amounts of sulphur is although stripped of by the processed coke-stove gas of wet desulfuration tower, but if does not drop to requirement also
Below scope, dry desulfurizing tower is preferably set to carry out further desulfurization again, dry desulfurizing tower is internally provided with a section fixation
Bed, fixed bed is fixed with activated carbon or ferric oxide desulfurizer is used for the further desulfurization of coke-stove gas.
Further, iron oxide desulphurization plant further includes humidistat 9, and the humidistat is arranged at the described 4th
On pipeline.Drier may be selected in humidistat, and the drier loaded in drier can select silica gel, activated carbon etc. corrosion-resistant
Drier.
Further, iron oxide desulphurization plant further includes clear liquid pump 10 and turbid pump 11, and the clear liquid pump is arranged at institute
State on second pipe, the turbid pump is arranged on the 3rd pipeline.In order to improve preferably circulation profit to clear liquid and turbid
With power, circulation of the clear liquid pump with turbid pump for clear liquid and turbid is preferably provided.
In the present invention, also complex iron oxide desulfurizing agent can be directly prepared into solid-state, by brown iron oxide and/or hydrated ferric oxide
Desulfurizing agent is mixed with strong acid weak base salt in the state of drying, is then mixed with adhesive columned solid multiple
Mould assembly desulfurizing agent, equipment supporting at this time can choose dry desulfurizing tower, i.e., a kind of packed tower, laminated desulfurizer is fixed on
In tower body, when regeneration, can select regenerated mode in tower, when the oxygen content in gas is insufficient, it is necessary to carry out outside tower again
It is raw, without influencing desulfurization in tower.
Illustrated below using specific embodiment：
Embodiment 1
Specific desulfurization process is as follows：
1) by the brown iron oxide and NH of commercially available acquisition4Cl solution carries out being mixed to form complex iron oxide desulfurizing agent, wherein oxygen
Change the iron ion and NH in iron powder4NH in Cl4 +Molar ratio be 1:1；
2) complex iron oxide desulfurizing agent is passed through from the up or down liquid distribution trough of wet desulfuration tower, and coke-stove gas then from
The downside of tower enters, and inversely contacts carry out desulfurization with desulfurizing agent, and there is a packing layer that two sections of fillers are Raschig ring in centre, in tower
Top is provided with reverse V-shaped fold-type porous plate.
Embodiment 2
Specific desulfurization process is as follows：
1) by brown iron oxide, hydrated ferric oxide desulfurizing agent and AlCl3Solution carries out being mixed to form complex iron oxide desulfurizing agent,
Iron ion and AlCl wherein in brown iron oxide3In Al3+Molar ratio be 100:1；
2) complex iron oxide desulfurizing agent is passed through from the up or down liquid distribution trough of wet desulfuration tower, and coke-stove gas then from
The downside of tower enters, and inversely contacts carry out desulfurization with desulfurizing agent, and there is a packing layer that two sections of fillers are Raschig ring in centre, in tower
Top is provided with reverse V-shaped fold-type porous plate；
3) coke-stove gas after wet desulphurization then enters in dry desulfurizing tower into one from tower top by humidistat
Desulfurization is walked, the complex iron oxide desulfurizing agent after desulfurization is returned again in wet desulfuration tower after then being regenerated into regenerating tank, is regenerated
Outside air is passed through bubbling in regenerating tank by using air pump and is regenerated by mode, and the material that regenerating tank tank bottom comes out passes through
Liquid phase then returns after filtering, heating, and solid phase is recycled for sulphur.
Embodiment 3
Specific desulfurization process is as follows：
1) by the hydrated ferric oxide desulfurizing agent and AlCl of commercially available acquisition3With FeCl3Mixed solution be mixed to form it is compound
Iron ion and AlCl in ferric oxide desulfurizer, wherein brown iron oxide3With FeCl3Mixed solution in cation molar ratio
For 90:1；
2) complex iron oxide desulfurizing agent is passed through from the up or down liquid distribution trough of wet desulfuration tower, and coke-stove gas then from
The downside of tower enters, and inversely contacts carry out desulfurization with desulfurizing agent, and there is a packing layer that two sections of fillers are ceramic ring in centre, in tower
Top is provided with reverse V-shaped fold-type porous plate；
3) coke-stove gas after wet desulphurization then enters in dry desulfurizing tower by drier from tower top and further takes off
Sulphur, drier selection silica gel, the complex iron oxide desulfurizing agent after desulfurization return again to wet method after then being regenerated into regenerating tank and take off
In sulphur tower, the supernatant liquor in regenerative process in regenerating tank is returned by clear liquid pump, and lower floor's turbid is pumped by turbid and returned, regeneration
Outside air is passed through bubbling in regenerating tank by using air pump and is regenerated by mode, and the material that regenerating tank tank bottom comes out passes through
Liquid phase then returns after strainer filtering, steam heating, and solid phase is recycled for sulphur.
Comparative example 1
Desulfurization is carried out using iron oxide dry method, iron oxide is directly fixed on to the inside of packed tower, forms filling out from level to level
Material, then coke-stove gas is entered carry out desulfurization from bottom of towe.
Experimental example 1
1-3 of the embodiment of the present invention is respectively adopted in coke-stove gas and the sulfur method of comparative example 1 carries out desulfurization, processing time
It is 15-20Nm3/ h, the initial sulfur content in coke-stove gas is 2000mg/Nm3, through measure after desulfurization process, embodiment 1
Coke-stove gas sulfur content is 80mg/Nm3, the coke-stove gas sulfur content in embodiment 2 is 20mg/Nm3, the coke-oven coal in embodiment 3
Gas sulfur content is 15mg/Nm3, the coke-stove gas sulfur content in comparative example 1 is 200mg/Nm3。
Can be seen that from above-mentioned data, when only with wet desulfuration tower of the present invention carry out desulfurization when, its desulfurization effect relative to
The prior art makes moderate progress, when the dry desulfurizing tower of the wet desulfuration tower of the present invention and the prior art is used in combination, its sulphur
Removal efficiency is then significantly larger than existing desulfurization technology.
Although being illustrated and the invention has been described with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (7)
1. a kind of iron oxide sulfur method, it is characterised in that include the following steps：
Desulfurizing agent and strong acid weak base salting liquid are mixed to form complex iron oxide desulfurizing agent, inversely contacts and is taken off with coke-stove gas
Sulphur；Wherein, the desulfurizing agent is one or both of brown iron oxide and hydrated ferric oxide desulfurizing agent；
The molar ratio of the cation in iron ion and strong acid weak base salt in the desulfurizing agent is 1-100:1；
After the complex iron oxide desulfurizing agent is inversely contacted progress desulfurization with coke-stove gas, the method further includes following step
Suddenly：Regenerated air is passed through for the complex iron oxide desulfurizing agent after desulfurization, and by the coke-stove gas after desulfurization using dry
Method desulfurization carries out further desulfurization.
2. iron oxide sulfur method according to claim 1, it is characterised in that in the strong acid weak base salt, cation is
NH4+、Mg2+、Al3+、Fe3+、Zn2+In one or more, anion SO4 2-、Cl-One or both of.
3. iron oxide sulfur method according to claim 1, it is characterised in that the iron oxide sulfur method is using as follows
Oxidation sweetening equipment, including：Wet desulfuration tower；The wet desulfuration tower includes tower body, is provided with the downside of the tower body side wall
Go out the liquid outlet of tower, the tower into the first air inlet of tower and for the complex iron oxide desulfurizing agent after desulfurization for coke-stove gas
The first gas outlet for going out tower for coke-stove gas is provided with the top of body, liquid distribution trough and lower liquid are provided with the tower body
Body distributor, the underface of the upper liquid distribution trough immediately below the lower liquid distribution trough with being separately provided for increasing
The packing layer of Gas-liquid interfacial area, the top in the tower body are provided with reverse V-shaped fold-type porous plate.
4. iron oxide sulfur method according to claim 3, it is characterised in that further include regenerating tank, air pump, the first pipe
Road, second pipe, the 3rd pipeline and air pipeline；Be respectively arranged with the side wall of the regenerating tank inlet, air intlet,
Purified liquor outlet and turbid outlet, the tank bottom of the regenerating tank are additionally provided with raffinate outlet；
The inlet is connected by the first pipeline with the liquid outlet, and the purified liquor outlet passes through second pipe and the upper liquid
The import connection of body distributor, the turbid outlet is connected by the 3rd pipeline with the import of the lower liquid distribution trough, described
The gaseous phase outlet of air pump is connected by pipeline with the air intlet.
5. iron oxide sulfur method according to claim 3, it is characterised in that further include dry desulfurizing tower and the 4th pipe
Road；The side wall of the dry desulfurizing tower be provided with the second air inlet and go out tower for reaching the coke-stove gas of desulfurization standard
Two gas outlets, wherein, second air inlet is connected by the 4th pipeline with first gas outlet.
6. iron oxide sulfur method according to claim 5, it is characterised in that further include humidistat, the humidity
Adjuster is arranged on the 4th pipeline.
7. iron oxide sulfur method according to claim 4, it is characterised in that further include clear liquid pump and turbid pump, institute
State clear liquid pump to be arranged on the second pipe, the turbid pump is arranged on the 3rd pipeline.
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