CN103468327A - Combined deamination desulphurization technology for coke oven gas - Google Patents
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Abstract
A combined deamination desulphurization technology for coke oven gas comprises: (1) reacting the coke oven gas with a ferrous sulphate solution to remove anmmonia in the coke oven gas, controlling the temperature at 20-40 DEG C and the pH of the solution at 5-9 in the reaction process, wherein a solution containing ammonium sulfate and fougerite is generated; (2) introducing an oxygen-containing gas into the solution containing ammonium sulfate and fougerite and generated in the step (1) to oxidize fougerite and generate FeOOH; and (3) filtering the oxidized solution and taking the filtered-out FeOOH as a desulfurizer in the step (2) to desulfurize the deaminated coke oven gas in the step (1). According to the technology, desulphurization of the coke oven gas, preparation of ammonium sulfate and preparation of the desulfurizer are combined together, and the byproduct generated during preparation of ammonium sulfate in the field of desulphurization deamination of the coke oven gas is utilized and helps to realize preparation of the desulfurizer, so that the desulfurizer does not need buying additionally, and the technology is improved in economic performance.
Description
Technical field
The invention belongs to the gas purification field, be specifically related to a kind of technique for coke-oven gas deamination, desulfurization.
Background technology
Coke-oven gas is the important by product produced in process of coking, and coke-oven gas is a kind of fuel source of preciousness, but, due in process of coking, in feed coal, the sulphur of about 30-35% can change into H
2the S sulfides, with HCN and the NH that in coke-oven gas, itself contains
3deng forming together poisonous, the detrimental impurity in coal gas, wherein alkaline gas NH
3pipe-line equipment is had to very strong corrodibility, sour gas H
2s and HCN also have very strong toxicity except severe corrosive, and coke-oven gas is at H wherein when the fuel
2the product S O that S and its burning generate
2all poisonous, so coke-oven gas must pass through purifying treatment acting as a fuel before using, and coke-oven gas carried out to deamination, desulfurization processing.Therefore and be of little use the method for processing ammonia in prior art has washing ammonia process, phosphorus ammonia process and ammonium sulfate method, wherein washes ammonia process, the phosphorus ammonia process is respectively used to prepare strong aqua and anhydrous ammonia, because energy consumption is huge.And traditional ammonium sulfate method sulfuric acid and ammonia react a large amount of because needs expend, the sulfuric acid price is higher again, therefore its economy is also bad, for this reason, start in recent years to utilize cheap ferrous sulfate to replace sulfuric acid to prepare ammonium sulfate, in order further to reduce production costs, also to have occurred utilizing the byproduct ferrous sulfate of titanium dioxide to prepare the technology of ammonium sulfate, thereby increased substantially the economic performance of the standby technique of ammonium sulfate legal system.
For the sulfur method of coke-oven gas, use the more of Fe-series desulfurizing agent in prior art, as Chinese patent literature CN1312350A discloses, utilize ferric oxide to remove the H in coke-oven gas
2the method of S; In order further to improve desulfuration efficiency, Chinese patent literature CN101584962 also discloses a kind of for removing the FeOOH desulfurizer of sulfide, this sweetening agent is by the amorphous hydrous iron oxide FeOOH of 50-95wt%, the carrier of 0-45wt%, the organic binder bond of 5-50wt% forms, this sweetening agent has higher Sulfur capacity and working strength, and sweetening effectiveness is better.
But the technique of above-mentioned deamination and desulfurization is independently to carry out, not only need to arrange desulfurization and deamination two cover techniques, also need to arrange independent technique for the preparation of Fe-series desulfurizing agent, therefore also more complicated of whole technique, equipment and running cost are higher, in order to realize deamination, sulfur removal technology integrated, Chinese patent literature CN1154998A discloses a kind of Desulphurization Technology Coke Oven Gas that utilizes ammonia process, this technique is passed through just cold by coke-oven gas, the air blast pressurization, electrically trapped tar oil, after precooling, with the sweetening agent reverse convection, move, in doctor solution under the effect of catalyzer, by chemical absorption, react, catalyzed chemical reaction, the catalytic regeneration oxidizing reaction removes hydrogen sulfide, use therein catalyzer is Resorcinol, phthalocyanine cobalt sulfonate, the composite catalyst of ferrous sulfate, the temperature of desulphurization reaction is 30-40 ℃, ammonia in this technology utilization coke-oven gas carries out desulfurization, also removed the ammonia in coal gas in desulfurization, realized deamination, sulfur removal technology integrated, and the product ammonium sulfate of ammonia desulfurizing process can be used as the fertilizer recycling, there is good environmental benefit.
But while utilizing the ammonia process of desulfurization to process coke-oven gas, in coke-oven gas, the ratio of ammonia and sulphur hour, needs the extra ammoniacal liquor that supplements, and its economy is also unsatisfactory.Therefore, how the preparation of the preparation of the desulfurization of coke-oven gas, ammonium sulfate and sweetening agent can be combined, further improve the economic performance of technique, be a still unsolved difficult problem of prior art.
Summary of the invention
Not only need to arrange desulfurization and deamination two cover techniques in order to solve coke-oven gas treatment process of the prior art, also need to arrange independent technique for the preparation of sweetening agent, whole technique more complicated, equipment and running cost are higher, and while utilizing the ammonia process of desulfurization to process coke-oven gas, in coke-oven gas, the ratio of ammonia and sulphur hour, also need additionally to supplement ammoniacal liquor, its economy is unsatisfactory problem also, the invention provides a kind of by the de-ammonium sulfate of coke-oven gas, the preparation of magister of sulfur and sweetening agent combines, economic performance is the technique of cog joint deamination and desulfurization preferably.
The technical scheme of the technique of the combining deamination and desulfurization for coke-oven gas of the present invention is:
A kind of technique of the combining deamination and desulfurization for coke-oven gas comprises:
(1) coke-oven gas is reacted to the ammonia removed in described coke-oven gas with copperas solution, controlling temperature in reaction process is 20-40 ℃, and pH is 5-9, and reaction generates the solution that contains ammonium sulfate and patina;
(2) pass into oxygen-containing gas in the middle solution that contains ammonium sulfate and patina generated of step (1), patina is carried out to oxidation and generate hydrous iron oxide;
(3) solution after oxidation is filtered, the hydrous iron oxide leached is carried out to desulfurization as sweetening agent to the coke-oven gas after step (1) deamination.
In described step (1), the concentration of copperas solution is 0.8mol/L-1.3mol/L, and the vapour-liquid ratio of described coke-oven gas and described copperas solution is 1.0-2.0.
In described step (2), in temperature, be 30-50 ℃, under the condition that pH is 6-8, patina carried out to oxidation and generate amorphous hydrous iron oxide.
In described step (2), in temperature, be 60-90 ℃, under the condition that pH is 2-4, patina carried out to oxidation and generate the Alpha-hydroxy ferric oxide.
In described step (2), in temperature, be 20-30 ℃, under the condition that pH is 2-4, patina carried out to oxidation and generate the beta-hydroxy ferric oxide.
In described step (2), in temperature, be 10-20 ℃, under the condition that pH is 4-6, patina carried out to oxidation and generate γ-hydrous iron oxide.
Count 0.2-1m to the speed that passes into oxygen-containing gas in every cubic metre of described solution with oxygen
3/ h.
Desulfurization temperature in described step (3) is 30-50 ℃.
In described step (3), described hydrous iron oxide and water are made into to the hydrous iron oxide slurries, utilize described hydrous iron oxide slurries, as sweetening agent, coke-oven gas is carried out to the drip washing desulfurization.
In described hydrous iron oxide slurries, the concentration of hydrous iron oxide is 10-15wt%.
To leaching solution after hydrous iron oxide in step (3), evaporated, crystallization, prepare ammonium sulfate.
To after pervaporation, crystallization, mix with hydrous iron oxide by the remaining aqueous solution, be made into the slurries in step (3).
Activate recovery to completing the useless agent of the hydrous iron oxide formed after desulfurization in step (3).
The technique of desulfurization deamination of the present invention, step (1) is reacted coke-oven gas the ammonia removed in described coke-oven gas with copperas solution, controlling temperature in reaction process is 20-40 ℃, and pH is 5-9, and reaction generates the solution that contains ammonium sulfate and patina; The concentration that the present invention limits described copperas solution is 0.8mol/L-1.3mol/L, and reason is that the too small meeting of the concentration of copperas solution is unfavorable for neutralization reaction; Although and concentration is conducive to neutralization reaction when high, but while having arrived the oxidation stage in subsequent step (3), the ferrous sulfate of high density can cause the solution thickness, make oxidizing reaction be difficult to carry out, and then affected the generation of hydrous iron oxide, the present invention is 0.8mol/L-1.3mol/L by the concentration that described copperas solution is set, and has effectively avoided above-mentioned two situations.The liquid-gas ratio that the present invention also limits described coke-oven gas and described copperas solution is 1.0-2.0, reason is that liquid-gas ratio is too little, can make desulphurization reaction incomplete, makes desulfuration efficiency low, and liquid-gas ratio is too large, can make again coke-oven gas be difficult to go out tower by liquid phase.
Step (2) passes into oxygen-containing gas in the middle solution that contains ammonium sulfate and patina generated of step (1), patina is carried out to oxidation and generate hydrous iron oxide; The present invention also limits generating the required reaction conditions of different crystal forms hydrous iron oxide: patina is a kind of unstable compound, in the process of oxidation patina, with the difference of pH value and temperature, its oxidation products can be α, β, γ, unformed-hydrous iron oxide or Fe
3o
4.The applicant finds in research, can control the generation of different shape hydrous iron oxide by the processing condition in the control oxidising process, being specially in temperature is 30-50 ℃, under the condition that pH is 6-8, patina is carried out to oxidation and generates amorphous hydrous iron oxide; Be 60-90 ℃ in temperature, under the condition that pH is 2-4, patina carried out to oxidation and generate the Alpha-hydroxy ferric oxide; Be 20-30 ℃ in temperature, under the condition that pH is 2-4, patina carried out to oxidation and generate the beta-hydroxy ferric oxide; Be 10-20 ℃ in temperature, under the condition that pH is 4-6, patina carried out to oxidation and generate γ-hydrous iron oxide.
Step (3) is filtered the solution after oxidation, and the hydrous iron oxide leached is carried out to desulfurization as sweetening agent to the coke-oven gas after step (1) deamination.In order to guarantee sweetening effectiveness, it is 30-50 ℃ that the present invention limits described desulfurization temperature.
The advantage of the technique of the combining deamination and desulfurization for coke-oven gas of the present invention is:
Combining deamination and desulfurization for coke-oven gas technique of the present invention, utilize copperas solution to carry out deamination to coke-oven gas, again coke-oven gas is reacted the solution that contains ammonium sulfate and patina generated with copperas solution and carry out oxidation, oxidation generates hydrous iron oxide, and the hydrous iron oxide leached is used as to the sweetening agent of coke-oven gas again.The present invention makes the desulfurization of coke-oven gas, the preparation of ammonium sulfate and the preparation of sweetening agent combine by described technique is set, at the scene of coke-oven gas deamination and desulfurization, utilize the by product produced while preparing ammonium sulfate can realize the preparation of sweetening agent, do not need additionally to buy again, from having improved the economic performance of technique.
The accompanying drawing explanation
For content of the present invention more easily is expressly understood, below in conjunction with specific embodiments and the drawings, content of the present invention is described in further detail, wherein
The schema that Fig. 1 is the technique of the combining deamination and desulfurization for coke-oven gas of the present invention;
The schema of the convertible mode that Fig. 2 is the technique of the combining deamination and desulfurization for coke-oven gas of the present invention.
Embodiment
embodiment 1
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 1, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, and controlling temperature in the ammonia absorber tower reactor is 40 ℃, and the pH of reaction soln is 9; The concentration of copperas solution is 0.8mol/L, and the liquid-gas ratio of described coke-oven gas and described copperas solution is 1.0, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, the control temperature of reaction is 50 ℃, and pH value of solution is 8, to the speed that passes into oxygen-containing gas in every cubic metre of described solution, with oxygen, counts 0.2m
3/ h, reaction generates amorphous hydrous iron oxide.
(3) solution after oxidation is filtered, the amorphous hydrous iron oxide and the water that leach are hybridly prepared into to the amorphous hydrous iron oxide slurries as sweetening agent, in described slurries, the concentration of hydrous iron oxide is 15wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 40 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 2
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 20 ℃, the pH of reaction soln is 5, the concentration of copperas solution is 1.3mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 2.0, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 40 ℃, and pH value of solution is 7, and the intake that contains the oxygen air in every cubic metre of solution is counted 0.2m with oxygen
3/ h, reaction generates amorphous hydrous iron oxide.
(3) solution after oxidation is filtered, the amorphous hydrous iron oxide and the water that leach are hybridly prepared into to the amorphous hydrous iron oxide slurries as sweetening agent, in described slurries, the concentration of hydrous iron oxide is 15wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 40 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 3
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 20 ℃, the pH of reaction soln is 5, the concentration of copperas solution is 1mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 1.5, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 60 ℃, and pH value of solution is 2, and the intake that contains the oxygen air in every cubic metre of solution is counted 0.3m with oxygen
3/ h, reaction generates the Alpha-hydroxy ferric oxide.
(3) solution after oxidation is filtered, the Alpha-hydroxy ferric oxide and the water that leach are hybridly prepared into to the Alpha-hydroxy iron oxide slurry as sweetening agent, in described slurries, the concentration of Alpha-hydroxy ferric oxide is 13wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 45 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 4
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 40 ℃, the pH of reaction soln is 9, the concentration of copperas solution is 0.8mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 1, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 90 ℃, and pH value of solution is 4, and the intake that contains the oxygen air in every cubic metre of solution is counted 1m with oxygen
3/ h, reaction generates the Alpha-hydroxy ferric oxide.
(3) solution after oxidation is filtered, the Alpha-hydroxy ferric oxide and the water that leach are hybridly prepared into to the Alpha-hydroxy iron oxide slurry as sweetening agent, in described slurries, the concentration of Alpha-hydroxy ferric oxide is 13wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 35 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 5
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling ammonia absorber tower reactor temperature is 20 ℃, the pH of reaction soln is 7, the concentration of controlling copperas solution is 1mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 1, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 70 ℃, and pH value of solution is 4, and the intake that contains the oxygen air in every cubic metre of solution is counted 0.5m with oxygen
3/ h, reaction generates the Alpha-hydroxy ferric oxide.
(3) solution after oxidation is filtered, the Alpha-hydroxy ferric oxide and the water that leach are hybridly prepared into to the Alpha-hydroxy iron oxide slurry as sweetening agent, in described slurries, the concentration of Alpha-hydroxy ferric oxide is 13wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 30 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 6
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 30 ℃, the pH of reaction soln is 7, the concentration of copperas solution is 1.2mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 1.5, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 20 ℃, and pH value of solution is 2, and the intake that contains the oxygen air in every cubic metre of solution is counted 1m with oxygen
3/ h, reaction generates the beta-hydroxy ferric oxide.
(3) solution after oxidation is filtered, the beta-hydroxy ferric oxide and the water that leach are hybridly prepared into to the beta-hydroxy iron oxide slurry as sweetening agent, in described slurries, the concentration of beta-hydroxy ferric oxide is 10wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 50 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 7
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 30 ℃, the pH of reaction soln is 6, the concentration of copperas solution is 1.3mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 2, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 30 ℃, and pH value of solution is 2, and the intake that contains the oxygen air in every cubic metre of solution is counted 0.8m with oxygen
3/ h, reaction generates the beta-hydroxy ferric oxide.
(3) solution after oxidation is filtered, the beta-hydroxy ferric oxide and the water that leach are hybridly prepared into to the beta-hydroxy iron oxide slurry as sweetening agent, in described slurries, the concentration of beta-hydroxy ferric oxide is 14wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 40 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 8
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 40 ℃, the pH of reaction soln is 6, the concentration of copperas solution is 0.8mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 1, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 30 ℃, and pH value of solution is 4, and the intake that contains the oxygen air in every cubic metre of solution is counted 0.4m with oxygen
3/ h, reaction generates the beta-hydroxy ferric oxide.
(3) solution after oxidation is filtered, the beta-hydroxy ferric oxide and the water that leach are hybridly prepared into to the beta-hydroxy iron oxide slurry as sweetening agent, in described slurries, the concentration of beta-hydroxy ferric oxide is 12wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 40 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 9
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 30 ℃, the pH of reaction soln is 5, the concentration of copperas solution is 0.9mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 1, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 10 ℃, and pH value of solution is 4, and the intake that contains the oxygen air in every cubic metre of solution is counted 0.9m with oxygen
3/ h, reaction generates γ-hydrous iron oxide.
(3) solution after oxidation is filtered, γ-hydrous iron oxide of leaching and water are hybridly prepared into to γ as sweetening agent-hydrous iron oxide slurries, in described slurries, the concentration of γ-hydrous iron oxide is 15wt%;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 30 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
embodiment 10
The technique of the combining deamination and desulfurization for coke-oven gas described in the present embodiment as shown in Figure 2, comprising:
(1) coke-oven gas is passed into to ammonia absorber, coke-oven gas is reacted with the copperas solution of ammonia absorber top spray the ammonia removed in described coke-oven gas, controlling temperature in the ammonia absorber tower reactor is 40 ℃, the pH of reaction soln is 5, the concentration of copperas solution is 1.1mol/L, the liquid-gas ratio of described coke-oven gas and described copperas solution is 1.2, and reaction generates the solution that contains ammonium sulfate and patina.
(2) to passing into oxygen-containing gas in the solution that contains ammonium sulfate and patina generated in step (1), patina is carried out to oxidation, controlling temperature of reaction is 20 ℃, and pH value of solution is 6, and the intake that contains the oxygen air in every cubic metre of solution is counted 1 m with oxygen
3/ h, reaction generates γ-hydrous iron oxide.
(3) solution after oxidation is filtered, γ-hydrous iron oxide of leaching and water are hybridly prepared into to γ as sweetening agent-hydrous iron oxide slurries, in described slurries, the concentration of γ-hydrous iron oxide is 11wt%; To leaching solution after γ-hydrous iron oxide, evaporated, crystallization, prepare ammonium sulfate;
Coke-oven gas after step (1) deamination is passed into to thionizer from bottom, and the temperature of described thionizer tower reactor is 30 ℃, and the top of described thionizer is carried out the drip washing desulfurization by the nozzle ejection sweetening agent to described coke-oven gas.
In the above-described embodiments, can be evaporated leaching solution after amorphous hydrous iron oxide, crystallization, prepare ammonium sulfate, after evaporation, crystallization, the remaining aqueous solution can be used for preparing the hydrous iron oxide slurries.
What the desulfurized step in above-described embodiment adopted is wet desulphurization, is about to hydrous iron oxide and water and is hybridly prepared into slurries as sweetening agent; As selectable embodiment, also can adopt dry desulfurization, soon the hydrous iron oxide solid is deposited in thionizer and carries out desulfurization, and heap specific density when described hydrous iron oxide solid is stacked is 0.9～1.0Kg/L, and the aspect ratio that solid is stacked in thionizer is set to 3-6.
In addition, the useless agent of the hydrous iron oxide in above-described embodiment, filtration obtained activates the method reclaimed and is: the useless agent of the described hydrous iron oxide that filtration is obtained is configured to the suspension of 10-20wt%, pass into oxygen-containing gas and carry out oxidation, make the iron sulfide in suspension be converted into hydrous iron oxide and elemental sulfur, remove elemental sulfur by flotation, the hydrous iron oxide after can being activated.
Obviously, above-described embodiment is only for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the invention.
Claims (13)
1. the technique of the combining deamination and desulfurization for coke-oven gas comprises:
(1) coke-oven gas is reacted to the ammonia removed in described coke-oven gas with copperas solution, controlling temperature in reaction process is 20-40 ℃, and pH is 5-9, and reaction generates the solution that contains ammonium sulfate and patina;
(2) pass into oxygen-containing gas in the middle solution that contains ammonium sulfate and patina generated of step (1), patina is carried out to oxidation and generate hydrous iron oxide;
(3) solution after oxidation is filtered, the hydrous iron oxide leached is carried out to desulfurization as sweetening agent to the coke-oven gas after step (1) deamination.
2. the technique of the combining deamination and desulfurization for coke-oven gas according to claim 1, it is characterized in that, in described step (1), the concentration of copperas solution is 0.8mol/L-1.3mol/L, and the vapour-liquid ratio of described coke-oven gas and described copperas solution is 1.0-2.0.
3. the technique of the combining deamination and desulfurization for coke-oven gas according to claim 1 and 2, is characterized in that, in described step (2), in temperature, is 30-50 ℃, under the condition that pH is 6-8, patina carried out to oxidation and generate amorphous hydrous iron oxide.
4. the technique of the combining deamination and desulfurization for coke-oven gas according to claim 1 and 2, is characterized in that, in described step (2), in temperature, is 60-90 ℃, under the condition that pH is 2-4, patina carried out to oxidation and generate the Alpha-hydroxy ferric oxide.
5. the technique of the combining deamination and desulfurization for coke-oven gas according to claim 1 and 2, is characterized in that, in described step (2), in temperature, is 20-30 ℃, under the condition that pH is 2-4, patina carried out to oxidation and generate the beta-hydroxy ferric oxide.
6. the technique of the combining deamination and desulfurization for coke-oven gas according to claim 1 and 2, is characterized in that, in described step (2), in temperature, is 10-20 ℃, under the condition that pH is 4-6, patina carried out to oxidation and generate γ-hydrous iron oxide.
7. according to the arbitrary described technique of the combining deamination and desulfurization for coke-oven gas of claim 1-6, it is characterized in that, to the speed that passes into oxygen-containing gas in every cubic metre of described solution, with oxygen, count 0.2-1m
3/ h.
8. according to the arbitrary described technique of the combining deamination and desulfurization for coke-oven gas of claim 1-7, it is characterized in that, the desulfurization temperature in described step (3) is 30-50 ℃.
9. according to the arbitrary described technique of the combining deamination and desulfurization for coke-oven gas of claim 1-8, it is characterized in that, in described step (3), described hydrous iron oxide and water are made into to the hydrous iron oxide slurries, utilize described hydrous iron oxide slurries, as sweetening agent, coke-oven gas is carried out to the drip washing desulfurization.
10. the technique of the combining deamination and desulfurization for coke-oven gas according to claim 9, is characterized in that, in described hydrous iron oxide slurries, the concentration of hydrous iron oxide is 10-15wt%.
11., according to the arbitrary described technique of the combining deamination and desulfurization for coke-oven gas of claim 1-10, it is characterized in that, to leaching solution after hydrous iron oxide in step (3), evaporated, crystallization, prepare ammonium sulfate.
12. the technique of the combining deamination and desulfurization for coke-oven gas according to claim 11, is characterized in that, will mix with hydrous iron oxide by the remaining aqueous solution after pervaporation, crystallization, is made into the slurries in step (3).
13. according to the arbitrary described technique of the combining deamination and desulfurization for coke-oven gas of claim 1-12, it is characterized in that, to completing the useless agent of the hydrous iron oxide formed after desulfurization in step (3), activate recovery.
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| CN106379945A (en) * | 2016-09-13 | 2017-02-08 | 北京三聚环保新材料股份有限公司 | Method for preparing ammonium sulfate coproduced iron oxyhydroxide |
| CN107572593A (en) * | 2017-09-15 | 2018-01-12 | 北京三聚环保新材料股份有限公司 | A kind of γ FeOOH preparation method |
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| CN101767829A (en) * | 2008-12-30 | 2010-07-07 | 北京三聚环保新材料股份有限公司 | Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same |
| CN101767776A (en) * | 2008-12-30 | 2010-07-07 | 北京三聚环保新材料股份有限公司 | Amorphous FeOOH and method for regenerating desulfurizing agent taking amorphous FeOOH as active ingredient |
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| US2880061A (en) * | 1955-06-20 | 1959-03-31 | Crucible Steel Co America | Process for recovering useful values from waste pickle liquor and raw coke oven gas |
| US3014785A (en) * | 1958-05-22 | 1961-12-26 | Crucible Steel Co America | Method of producing ammonium sulfate from coke oven gas and waste ferrous sulfate pickle liquor |
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