CN102965158B - The sulfur method of coke-oven gas - Google Patents
The sulfur method of coke-oven gas Download PDFInfo
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Abstract
The invention provides the sulfur method of the coke-oven gas of the concentration of the picric acid reduction resultant can known rapidly in desulfurization system.This sulfur method is that the alkaline aqueous solution that a kind of use contains picric acid reduction resultant carries out the Various Desulphurizing Methods of Coke-oven Gas of desulfurization to coke-oven gas, comprises the following steps: step Y with step X-1, step X-2, step X-3 and step X-4 for one group and the picric acid repeated outside the picric amount that repeatedly obtains adding in desulfurization system and discharge system reduce resultant amount between dependency; Step Z, based on the dependency of step Y gained, the picric amount of adding in desulfurization system, the picric amount be discharged to outside desulfurization system, tries to achieve the picric acid reduction resultant concentration in desulfurization system.
Description
Technical field
The present invention relates to the sulfur method of coke-oven gas.
Background technology
In the past, destructive distillation was being carried out in the operation manufacturing coke to coal, producing coke-oven gas.In such coke-oven gas, due to containing the hydrogen sulfide deriving from sulphur composition contained in coal, if directly used as fuel, the oxysulfide (SOx) deriving from hydrogen sulfide can be produced, to environmental effects.So, want to use coke-oven gas as fuel, just must carry out the removal of hydrogen sulfide before combustion.
As above-mentioned sulfur method, widely used method is, will contain the NH as absorption agent
4oH contacts with coke-oven gas with the picric alkaline aqueous solution (hereinafter also referred to " absorption liquid ") as desulfurization catalyst, by hydrogen sulfide with sulphur hydrogenation ammonia (NH
4sH) form absorbs, and changes this sulphur hydrogenation ammonia oxidation into sulphur by picric acid.
In above-mentioned sulfur method, the sulphur produced and picric in a part in thionizer, become mud and pile up on weighting agent.Therefore, because the pressure-losses in thionizer rises, the fan of subtend thionizer conveying coke-oven gas is applied with excessive load or can causes the bias current of coke-oven gas in thionizer sometimes, thus reduces desulfuration efficiency.
In order to suppress the sulphur in thionizer and picric accumulation, as long as the sulphur reduced in absorption liquid and picric acid concentration.Therefore, as long as suppress picric surplus to be added.On the other hand, reduce necessarily (excessively reducing) if the picric acid concentration in absorption liquid is performed for more than, then can reduce desulfuration efficiency.Therefore, require the picric acid concentration in absorption liquid to remain on desired value for a long time.
In the past, the addition of picric acid in absorption liquid exported according to thionizer concentration of hydrogen sulfide, the analytical results of the composition of coal that loads in coke oven adjust.But when the sulphur of such as separating out in separation, reclaiming tower etc., absorption liquid can be discharged to outside desulfurization system, and therefore, in above-mentioned picric addition means, the risk of the picric acid deviation of concentration desired value in absorption liquid is higher.
In the past, also there is the measurement result of the pressure-losses based on the coke-oven gas in thionizer, at the top of tower of thionizer, spray droplet mean diameter is the sulfur method (for example, referring to patent documentation 1) of the coke-oven gas of the alkaline aqueous solution of more than 5mm.
The sulfur method of the coke-oven gas recorded in patent documentation 1, the contact efficiency of absorption liquid and coke-oven gas is reduced by the liquid droplet diameter increasing absorption liquid, while the generation of the sulphur in the packing layer suppressing thionizer topmost, the clean effect of the packing layer produced by the absorption liquid drop that diameter is large prevents the accumulation of the sulphur mud of the local in the packing layer of thionizer topmost.
Prior art document
Patent documentation:
Patent documentation 1: Japanese Unexamined Patent Publication 2001-271074 publication
Summary of the invention
Invent problem to be solved
But, in the sulfur method of coke-oven gas described in patent documentation 1, owing to being adjust liquid droplet diameter based on the measurement result of the pressure-losses of the coke-oven gas in thionizer, bin cure there occurs accumulation to a certain degree and the pressure-losses and rises and start just to adjust liquid droplet diameter.Therefore, after adjustment liquid droplet diameter, until during the pressure-losses reaches suitable value, the problem remained in operation under having the state risen in the pressure-losses.In addition, generally speaking, the above-mentioned pressure-losses is the rising accelerated, even if adjust liquid droplet diameter from the pressure-losses rises, also exists and has enough time to suppress sulphur to generate completely, clean the problem of packing layer.
The concentration of picric acid self generally can use UV, visible light extinction photometer to measure.But, even if measured the picric acid concentration in the absorption liquid used in the desulfurization of coke-oven gas by UV, visible light extinction photometer, also can only trace be observed.This is because in absorption liquid, picric acid almost all with reduce resultant state exist.Therefore, the urgent method comprising the whole picric concentration of reduction resultant of wishing in the absorption liquid used in the desulfurization of exploitation mensuration coke-oven gas.
The present invention proposes in view of above-mentioned problem, and its object is to provides a kind of sulfur method promptly can knowing the coke-oven gas of the concentration of the reduction of the picric acid in desulfurization system resultant.
Solve the means of problem
In order to realize above object, the invention provides following methods.
A sulfur method for coke-oven gas, is the sulfur method of the coke-oven gas by the alkaline aqueous solution containing picric acid reduction resultant, coke-oven gas being carried out to desulfurization, it is characterized in that, comprise the following steps:
Absorption liquid is discharged outside desulfurization system by step X-1;
Step X-2 obtains the concentration by the picric acid reduction resultant in the absorption liquid outside above-mentioned steps X-1 discharge desulfurization system;
Step X-3, based on the amount of the absorption liquid of picric acid reduction resultant concentration and the discharge calculated by above-mentioned steps X-2, obtains the picric acid be expelled to outside desulfurization system and reduces the amount of resultant;
Step X-4 adds the picric acid of the amount based on empirical rule in desulfurization system;
Step Y with above-mentioned steps X-1, above-mentioned steps X-2, above-mentioned steps X-3 and the above-mentioned steps X-4 picric acid repeated for one group outside the picric amount that repeatedly obtains adding in desulfurization system and discharge system reduce resultant amount between dependency; And
Step Z, based on the amount of the described dependency according to above-mentioned steps Y gained, the picric amount of adding in desulfurization system, the absorption liquid be discharged to outside desulfurization system, tries to achieve the picric acid reduction resultant concentration in desulfurization system.
The present inventor finds, it is relevant that the picric amount of adding in desulfurization system and the picric acid outside discharge desulfurization system reduce the amount of resultant.And expect, if use this to be correlated with, by the picric amount of adding in desulfurization system and the amount of discharging the absorption liquid outside desulfurization system, the concentration of the picric acid reduction resultant in (extrapolating) desulfurization system can be obtained.
According to above-mentioned formation, if in advance with above-mentioned steps X-1, above-mentioned steps X-2, above-mentioned steps X-3 and the above-mentioned steps X-4 picric acid repeated for one group outside the picric amount that repeatedly obtains adding in desulfurization system and discharge system reduce resultant amount between dependency (in advance implementation step Y), then based on the amount of the described dependency according to above-mentioned steps Y gained, the picric amount of adding in desulfurization system, the absorption liquid be discharged to outside desulfurization system, picric acid reduction resultant concentration (step Z) in desulfurization system can be tried to achieve.That is, according to above-mentioned formation, even if impractically the absorption liquid sampled in desulfurization system measures the concentration of picric acid reduction resultant, the concentration of the picric acid reduction resultant in desulfurization system can also be learnt.Its result, promptly can know the concentration of the picric acid reduction resultant in desulfurization system.
In the above-described configuration, described step X-2 is preferably containing following steps:
Organic step is extracted from the absorption liquid of discharging;
Extract is carried out to the step of ultimate analysis:
Extract is carried out to the step of infrared spectroscopic analysis; And
The step of the picric acid reduction resultant concentration in described absorption liquid is obtained based on the result of above-mentioned ultimate analysis and the result of above-mentioned infrared spectroscopic analysis.
As mentioned above, picric acid nearly all exists as reduction resultant in absorption liquid.But, also do not know now the measuring method of the concentration of picric acid reduction resultant.
In the absorption liquid used in the desulfurization of coke-oven gas, containing picric acid reduction resultant (picric acid containing minute quantity itself), the aliphatic hydrocarbon being derived from tar contained in coke-oven gas, the aromatic hydrocarbons being derived from above-mentioned tar, thiocyanic acid amine, elemental sulfur and water-soluble substances.
According to above-mentioned formation, extract from absorption liquid with organism is that the material of main component is (following, if no special instructions, simply be called " organism "), while ultimate analysis is carried out to extract, infrared spectroscopic analysis is carried out to extract, based on the result of ultimate analysis and the result of infrared spectroscopic analysis, the concentration of picric acid reduction resultant (comprising the picric acid of minute quantity itself) can be obtained.Such as (a) is according to the whole organic concentration determined from the organic weight of absorption liquid extraction absorption liquid, b () determines the concentration of free sulphur according to ultimate analysis, c () determines the concentration of the material beyond free sulphur and picric acid reduction resultant according to infrared spectroscopic analysis, d () deducts the concentration of the material beyond the concentration of free sulphur and picric acid reduction resultant from whole organic concentration, can obtain the concentration of picric acid reduction resultant (comprising the picric acid of minute quantity itself) thus.
In above-mentioned formation, described step X-2 preferably includes following steps:
Steps A carries out UV absorbance analysis to the absorption liquid of discharging,
Step B from carried out UV absorbance analyze after absorption liquid extraction organism,
Step C carries out UV absorbance analysis to the absorption liquid extracted after organism,
Step D carries out ultimate analysis to extract,
Step e carries out infrared spectroscopic analysis to extract,
Step F based in above-mentioned steps A UV absorbance analyze result and above-mentioned steps C in UV absorbance analyze result, obtain in organism picric acid reduction resultant percentage extraction,
Step G, based on the result of the infrared spectroscopic analysis in the result of the ultimate analysis in above-mentioned steps D and above-mentioned steps E, is extracted the concentration of the reduction of the picric acid before rate conversion resultant,
The percentage extraction that the concentration of the picric acid reduction resultant before step H converts from the percentage extraction that above-mentioned steps G obtains and above-mentioned steps F obtain, obtains the concentration of picric acid reduction resultant.
The discoveries such as the present inventor, if observe the spectrum of absorption liquid with UV, visible light extinction photometer, although do not observe the spectrum of picric acid self, observe the spectrum having peak near 475nm, it is relevant that absorbancy and the picric acid of this 475nm reduce the concentration of resultant.
According to above-mentioned formation, UV absorbance analysis (steps A) is carried out for the absorption liquid of discharging, from absorption liquid extraction organism (step B) carried out after UV absorbance analysis, UV absorbance analysis (step C) is carried out to the absorption liquid after extraction organism.
The absorbancy at the 475nm place of absorption liquid and picric acid is utilized to reduce the relevant this point of concentration of resultant, based in above-mentioned steps A UV absorbance analyze result and above-mentioned steps C in UV absorbance analyze result, draw in organism picric acid reduction resultant percentage extraction (step F).
In addition, while ultimate analysis (step D) is carried out to extract, infrared spectroscopic analysis (step e) is carried out to extract, based on the result of ultimate analysis and the result of infrared spectroscopic analysis, the concentration (step G) of the picric acid reduction resultant before the percentage extraction obtained converts.Such as (a) is according to the whole organic concentration determined from the organic weight of absorption liquid extraction absorption liquid, b () determines the concentration of free sulphur according to ultimate analysis, c () determines the concentration of the material beyond free sulphur and picric acid reduction resultant according to infrared spectroscopic analysis, d () deducts the concentration of the material beyond the concentration of free sulphur and picric acid reduction resultant from whole organic concentration, obtain thus percentage extraction convert before the concentration of picric acid reduction resultant.
Then, according to the percentage extraction that concentration and the above-mentioned steps F of the picric acid reduction resultant before the percentage extraction conversion that above-mentioned steps G obtains obtain, the concentration (step H) of picric acid reduction resultant is obtained.
So, according to above-mentioned formation, can draw consider extraction organic step in be not extracted (remaining in aqueous phase) picric acid reduction resultant, more accurately picric acid reduction resultant concentration.
In the above-described configuration, preferably containing following steps, the picric acid reduction resultant concentration in the desulfurization system of namely trying to achieve according to described step Z adjusts picric addition.
According to above-mentioned formation, the concentration based on the picric acid reduction resultant in the desulfurization system of being tried to achieve by above-mentioned steps Z adjusts picric addition.Therefore, self-absorption liquid can be reduced and discharge desulfurization system outward to the time waste obtained this picric acid reduction resultant concentration.Its result, can adjust the concentration of the picric acid reduction resultant in absorption liquid in desired pre-determined range.Thus, the sulphur in thionizer can be suppressed to generate, the steady running of thionizer can be contributed to.
Invention effect
According to the present invention, the concentration of the picric acid reduction resultant in desulfurization system promptly can be known.
Accompanying drawing explanation
Fig. 1 is the system diagram of an example of the coke oven gas desulfurization equipment shown in analog in present embodiment.
Fig. 2 is the schema of the organic process in display extraction absorption liquid.
Fig. 3 is the schema of the dosing process of display aliphatic hydrocarbon.
Fig. 4 is the schema of the dosing process of display ammonium thiocyanate.
Fig. 5 is the absorption spectrum obtained in the ultraviolet radiation absorption analysis before display Solid-Phase Extraction, the figure of an example of absorption spectrum obtained in ultraviolet radiation absorption analysis after Solid-Phase Extraction.
Fig. 6 is the figure that the infrared absorption spectrum of the extract of octadecane is added in display.
Fig. 7 is the typical curve for quantitative aliphatic hydrocarbon.
Fig. 8 is the figure that display with the addition of the infrared absorption spectrum of the extract of ammonium thiocyanate.
Fig. 9 is the typical curve for quantitative ammonium thiocyanate.
Figure 10 is the figure of the relation curve between the concentration (concentration of the picric acid reduction resultant after percentage extraction conversion) of the picric acid reduction resultant measured in display embodiment 1 ~ 9 and the picric acid amount of adding.
Figure 11 is the figure of the picric acid reduction concentration of resultant before the percentage extraction in display embodiment 1 ~ 9 converts and the relation curve between the picric acid amount of interpolation.
Figure 12 to draw the figure of the relation curve obtained to add picric amount in desulfurization system to for y-axis to discharge picric acid amount outside desulfurization system for x-axis in display embodiment 1 ~ 9.
Description of reference numerals
10 coke oven gas desulfurization equipment
12 thionizers
13 pipe arrangements
14 regenerator columns
16 pipe arrangements
17 pipe arrangements
18 desulfurization waste liquor treatment unit
22 weighting agents
S1 stopple coupon
The interpolation of S2 catalyzer is managed
S3 stopple coupon
Pi picric acid
COG1 coke-oven gas
COG2 desulfurization coke-oven gas
A air
Embodiment
Below, for embodiments of the present invention, illustrate with reference to accompanying drawing.
Fig. 1 is the system diagram of the pattern of an example of the coke oven gas desulfurization equipment shown in present embodiment.Coke oven gas desulfurization equipment 10 has thionizer 12, regenerator column 14 and desulfurization waste liquor treatment unit 18.In coke oven gas desulfurization equipment 10, as absorption liquid, use containing the NH as absorption agent
4the aqueous solution of OH and the alkalescence as picric acid reduction resultant (comprising a small amount of picric acid self) of desulfurization catalyst.
In thionizer 12, from the top-spray absorption liquid of thionizer 12, when the below from thionizer 12 imports coke-oven gas COG1, the surface of the weighting agent 22 of then filling in thionizer 12, hydrogen sulfide in coke-oven gas COG1, prussic acid are absorbed in absorption liquid and removes, become desulfurization coke-oven gas COG2, be discharged to subsequent step from top.Now, hydrogen sulfide is as sulphur hydrogenation ammonia (NH
4sH) absorbed, prussic acid is as ammonium thiocyanate (NH
4sCN) absorbed.In addition, the picric acid as catalyzer is reduced, nitro (-NO
2) change nitroso-group (-NO), hydroxylamino (-NHOH) into.
Absorb hydrogen sulfide, prussic acid and containing picric acid reduction resultant absorption liquid, by being recovered at the bottom of the tower of thionizer 12, be delivered to regenerator column 14 through pipe arrangement 13.
Pipe arrangement 13 is connected with stopple coupon S1, can sample the absorption liquid of the recovery at the bottom of the tower from thionizer 12.
In regenerator column 14, import air A by the bottom of tower, the hydrogen sulfide absorbed in absorption liquid is separated out with free sulphur in liquid.In addition, picric acid reduction resultant also contacts with by the air A imported at the bottom of tower and oxidized, and meanwhile, alkali is reproduced, and is delivered to thionizer 12 once again through pipe arrangement 16.Thus, catalyzer and alkali are all recycled.
Pipe arrangement 16 is connected with stopple coupon S3, can sample the absorption liquid being transported to thionizer 12 from regenerator column 14.In addition, pipe arrangement 16 is connected with catalyzer interpolation pipe S2, can add picric acid Pi in absorption liquid.
In addition, regenerator column 14 is connected with pipe arrangement 17, in order to prevent accumulating precipitate in regenerator column 14, by the precipitate such as free sulphur, ammonium thiocyanate and absorption liquid simultaneously from it portion discharge, after by separation such as free sulphurs, be delivered to desulfurization waste liquor treatment unit 18.
In the sulfur method of present embodiment, as mentioned above, a part for absorption liquid is discharged to outside desulfurization system.In addition, as the picric acid of catalyzer, then the nitro (-NO when being reduced
2) nitroso-group (-NO), hydroxylamino (-NHOH) can be changed into, if but be reduced to amino (-NH further
2), be then difficult to regeneration, lose the effect of catalyzer.In order to make up this point, the absorption liquid circulated in desulfurization system can discharge a wherein part termly, and supplements new absorption liquid.Therefore, the picric acid concentration in the absorption liquid in desulfurization system changes.
In the sulfur method of present embodiment, carrying in the way of pipe arrangement 16 of absorption liquid from regenerator column 14 to thionizer 12, adding picric acid Pi.Now, the addition of picric acid Pi, the picric amount of adding in desulfurization system and the picric acid be expelled to outside desulfurization system reduce resultant amount between obtain relevant till, decide (step X-4) based on empirical rule.Then, the picric amount of adding in desulfurization system and the picric acid be expelled to outside desulfurization system reduce resultant amount between obtain relevant after, based on the amount of the dependency of gained, the picric amount of adding in desulfurization system, the absorption liquid be discharged to outside desulfurization system, try to achieve picric acid reduction resultant concentration (step Z) in desulfurization system, the concentration of the picric acid reduction resultant in the desulfurization system of trying to achieve according to there being above-mentioned steps Z, decides.It should be noted that, the picric amount of adding in desulfurization system and the picric acid be expelled to outside desulfurization system reduce resultant amount between obtain relevant after, the addition of picric acid Pi also can decide based on empirical rule.Even if in this case, owing to having tried to achieve the concentration of the picric acid reduction resultant in desulfurization system, such as, be equivalent to adjust the amount of the absorption liquid be discharged to outside desulfurization system, can by the concentration adjustment of the picric acid reduction resultant in absorption liquid in desired pre-determined range.
Below, first to obtain the picric amount of adding in desulfurization system and the picric acid be discharged to outside desulfurization system reduce resultant amount between the method for dependency be described.It should be noted that, this dependency can obtain while carrying out operation (desulfurization of coke-oven gas).
First, absorption liquid is discharged desulfurization system outer (step X-1).This step X-1 is undertaken by pipe arrangement 17.It should be noted that, the two or more in pipe arrangement, stopple coupon S1, stopple coupon S3 can be used to be discharged to outside desulfurization system by absorption liquid.
Then, try to achieve by the concentration (step X-2) of the picric acid reduction resultant in the absorption liquid outside step X-1 discharge desulfurization system.Discharged the concentration of the picric acid reduction resultant in the absorption liquid outside desulfurization system by step X-1, the concentration the absorption liquid drawn from pipe arrangement 17 can be adopted, also can adopt the concentration in the absorption liquid sampled by stopple coupon S1 or stopple coupon S3.But, therefore there is the situation of picric acid reduction resultant concentration generation difference in form (degree of oxidation) difference of compound according to the position of sampling.Therefore, preferably sample position is fixed on a place.Trying to achieve after method of concentration for the picric acid reduction resultant in the absorption liquid be discharged to outside desulfurization system is described in detail.
Then, based on the amount of the absorption liquid of picric acid reduction resultant concentration and the discharge of being tried to achieve by above-mentioned steps X-2, try to achieve the picric acid be discharged to outside desulfurization system and reduce the amount (step X-3) of resultant.Specifically, the amount of the picric acid reduction resultant be discharged to outside desulfurization system is obtained according to following formula.
(being discharged to the amount of the picric acid reduction resultant outside desulfurization system)=(the picric acid reduction resultant concentration of being tried to achieve by step X-2) × (amount of the absorption liquid of discharge)
On the other hand, the picric acid of the amount based on empirical rule is added in desulfurization system (step X-4).The picric amount of adding in step X-4, empirically determines from the redox potential equivalence of the proterties (concentration of hydrogen sulfide) of carbon loaded, desulfuration efficiency, absorption liquid.
Then, with above-mentioned steps X-1, above-mentioned steps X-2, above-mentioned steps X-3 and the above-mentioned steps X-4 picric acid repeated for one group outside the picric amount that repeatedly obtains thus adding in desulfurization system and discharge system reduce resultant amount between dependency (step Y).The repetition of above-mentioned steps X-1, above-mentioned steps X-2, above-mentioned steps X-3 and above-mentioned steps X-4 such as, can be carry out in 1 cycle with 1 month.Such as, the data that can obtain by repeatedly repeating above-mentioned steps obtain relational expression.
Then, the concrete example (concrete example of above-mentioned steps X-2) of the measuring method of the concentration of the picric acid reduction resultant in absorption liquid is described.
In the absorption liquid (hereinafter also referred to doctor solution) that coke oven gas desulfurization uses, containing the aliphatic hydrocarbon (hereinafter also referred to aliphatic hydrocarbon D) being derived from tar, the aromatic hydrocarbons (hereinafter also referred to aromatic hydrocarbons E) being derived from above-mentioned tar, ammonium thiocyanate (hereinafter also referred to ammonium thiocyanate C), elemental sulfur (hereinafter also referred to elemental sulfur B) and water-soluble substances contained in picric acid reduction resultant (hereinafter also referred to picric acid reduction resultant F), coke-oven gas.That is, B ~ F and water-soluble substances is contained in doctor solution.
In the measuring method of the concentration of the picric acid reduction resultant in above-mentioned absorption liquid, first UV absorbance analysis (steps A) is carried out to the absorption liquid of sampling.Then, solid-phase extraction column is used only to reclaim organism (step B).Thus, the water-soluble substances in above-mentioned B ~ F and water-soluble substances is removed.Then, by its vacuum-drying is extracted thing (hereinafter also referred to extract A).At this moment, the aromatic hydrocarbons E being derived from tar that boiling point is low, volatility is high is removed.Thus, containing above-mentioned B ~ D and above-mentioned F in extract A.But in picric acid reduction resultant F, because the wetting ability of the picric acid reduction resultant reduced strengthens, therefore, a part wherein cannot be extracted (moving to aqueous phase).
Then, UV absorbance analysis (step C) is carried out for the absorption liquid extracted after organism.It is relevant that absorbancy and the picric acid at 475nm place reduce the concentration of resultant.Thus, based in above-mentioned steps A UV absorbance analyze result (namely, absorbancy based on the whole picric acid reduction resultants in test portion) and above-mentioned steps C in UV absorbance analysis result (namely, absorbancy based on the picric acid be not extracted through the step B reduction resultant in test portion), obtain the percentage extraction (step F) of the picric acid reduction resultant in organism.
Then, by following method, obtain the concentration of the reduction of the picric acid before based on the conversion of percentage extraction resultant F.
I () weighing extract A, according to the amount of the doctor solution passed through in solid-phase extraction column and the weight of extract A, obtains the concentration (mg/L) of the extract A in doctor solution.
(ii) use Atomic Absorption SpectrophotometerICP, carry out the ultimate analysis of extract A, obtain concentration (mg/L) (the step D) of elemental sulfur B.
(iii) tablet containing extract A is made, by the infrared absorption spectrum by FT-IR (Fourier transform infrared spectrophotometer), obtain concentration (mg/L) (step e) of the aliphatic hydrocarbon D contained in extract A.
(iv) tablet containing extract A is made, by the infrared absorption spectrum by FT-IR (Fourier transform infrared spectrophotometer), obtain concentration (mg/L) (step e) of the ammonium thiocyanate C contained in extract A.
V (), based on the result of above-mentioned (i) ~ (iv) gained, obtains the concentration (step G) of the reduction of the picric acid before based on the conversion of percentage extraction resultant F by following calculating formula.
(concentration based on the picric acid reduction resultant F before the conversion of percentage extraction)=(concentration of extract A)-(concentration of elemental sulfur B)-(concentration of aliphatic hydrocarbon D)-(concentration of ammonium thiocyanate C)
Then, finally, according to the percentage extraction that concentration and the above-mentioned steps F of the picric acid reduction resultant F before the percentage extraction conversion that above-mentioned steps G obtains obtain, the concentration (step H) of picric acid reduction resultant is obtained.
Thus, can obtain considering (remaining in aqueous phase) picric acid reduction resultant of not being extracted in the organic step of extraction (step B), the concentration of the resultant of picric acid reduction more accurately.
Below, said determination method is described in detail in detail.
Fig. 2 is the schema of the organic process of extraction in display absorption liquid.
First, in step s 11, from stopple coupon S3, doctor solution is sampled.Then, in step s 12, use pure water to be diluted to 20 times to doctor solution 150ml, make test portion.
Then, in step s 13, UV absorbance analysis (steps A) is carried out to test portion.Obtain the absorbancy at 475nm place thus.
Then, in step S14, make test portion by solid-phase extraction column, make Adsorption of Organic.Now, the test portion by solid-phase extraction column is reclaimed.As solid-phase extraction column, can adopt known.As the weighting agent used in above-mentioned solid phase column extractor, as long as the organism in energy adsorption desulfurize liquid, be not particularly limited, such as polystyrene resin etc. can be exemplified.
Then, in step S15, solid-phase extraction column pure water is washed, remove water-soluble substances from solid-phase extraction column.
Then, in step s 16, will be passed through once again by solid-phase extraction column test portion once, so as absorption first time pass through in not by the organism adsorbed.
Then, in step S17, carry out UV absorbance analysis (step C) for by the test portion after solid-phase extraction column.Thus, the absorbancy at 475nm place is obtained.
Then, in step S18, in solid-phase extraction column, inject the methyl alcohol of 150ml, make the organism of absorption by stripping wash-out.
Then, concentrate eluant (step S19) in a rotary evaporator, afterwards, by enriched material dry 48 hours (step S20) in the Vacuumdrier of 70 DEG C.Thus, thing A is extracted.
At this moment, weigh by the amount of the extract A of above-mentioned extraction process gained, calculate the concentration of extract A.Afterwards, use Atomic Absorption SpectrophotometerICP to carry out the ultimate analysis of extract A, obtain the concentration (mg/L) of elemental sulfur B.In addition, by following process (with reference to Fig. 3, Fig. 4) carry out aliphatic hydrocarbon quantitatively and ammonium thiocyanate quantitative.
Fig. 3 is the schema of the dosing process of display aliphatic hydrocarbon.
First, using iron cyanogen (II) sour potassium (K as internal standard of the Potassium Bromide (KBr) of 10g with 2.12mg
4[Fe (CN)
6]) be dissolved in (step S21) in 300ml deionized water.
Then, concentrated in vaporizer, so dry in Vacuumdrier (60 DEG C, 24 hours), remove moisture (step S22).
Then, the octadecane agate mortar of the extract A:10mg extracted in the KBr:1g adding internal standard modulated in step S21, S22, above-mentioned extraction process and the specified amount that is dissolved in acetone is carried out mixing (step S23).
Then, mixture is dry in Vacuumdrier (60 DEG C, 24 hours), remove acetone (step S24), be shaped to tablet (step S25).
Then, use shaping tablet, carry out FT-IR mensuration (step S26).Now, the area ratio ((area of CH key)/(area of CN triple bond)) of the absorption spectrum of the absorption spectrum obtaining the CH key being derived from aliphatic hydrocarbon D and the CN triple bond being derived from internal standard material.
Then, change the use level of octadecane, shaping tablet as described above, carries out FT-IR mensuration (step S27).Now, same with step S26, the area ratio of the absorption spectrum of the absorption spectrum obtaining the CH key being derived from aliphatic hydrocarbon D and the CN triple bond that is derived from internal standard material.It should be noted that, the exactness of the typical curve made from the view point of later step S28, preferably while the use level changing octadecane, repeatedly carry out step S27.
Then, with the addition of octadecane be x-axis, above-mentioned area ratio is for y-axis production standard curve (step S28).
Then, according to the typical curve made, obtain the ratio of the aliphatic hydrocarbon D in extract A, by this ratio, calculate the concentration (step S29) of the aliphatic hydrocarbon D in doctor solution.It should be noted that, detailed method of calculation are shown in embodiment.
Fig. 4 is the schema of the dosing process of display ammonium thiocyanate.
It should be noted that, in the dosing process of ammonium thiocyanate illustrated below, except the octadecane (with reference to step S23) of mixing in the dosing process (with reference to Fig. 3) being replaced aliphatic hydrocarbon by ammonium thiocyanate, calculate the concentration of ammonium thiocyanate C with the process same with the dosing process of aliphatic hydrocarbon.
First, using the K as internal standard of KBr and 2.12mg of 10g
4[Fe (CN)
6] be dissolved in (step S31) in 300ml deionized water.
Then, concentrated in vaporizer, dry in Vacuumdrier (60 DEG C, 24 hours) further, remove moisture (step S32).
Then, by ammonium thiocyanate agate mortar mixing (step S33) of the extract A:10mg extracted in the KBr:1g adding internal standard modulated in step S31, S32, above-mentioned extraction process and the specified amount that is dissolved in acetone.
Then, mixture is dry in Vacuumdrier (60 DEG C, 24 hours), remove acetone (step S34), be shaped to tablet (step S35).
Then, use shaping tablet, carry out FT-IR mensuration (step S36).Now, the area ratio ((area of CN double bond)/(area of CN triple bond)) of the absorption spectrum of the absorption spectrum obtaining the CN double bond being derived from ammonium thiocyanate C and the CN triple bond being derived from internal standard material.
Then, change the use level of ammonium thiocyanate, be shaped to tablet as described above, carry out FT-IR mensuration (step S37).Now, same with step S36, the area ratio of the absorption spectrum of the absorption spectrum obtaining the CN double bond being derived from ammonium thiocyanate C and the CN triple bond that is derived from internal standard material.It should be noted that, the exactness of the typical curve made from the view point of step S38 subsequently, preferably while the use level changing ammonium thiocyanate, repeatedly carry out step S37.
Then, with the addition of ammonium thiocyanate be x-axis, with above-mentioned area ratio for y-axis, make typical curve (step S38).
Then, according to the typical curve made, obtain the ratio of the ammonium thiocyanate C in extract A, calculate the concentration (step S39) of the ammonium thiocyanate C doctor solution from this ratio.It should be noted that, detailed method of calculation are shown in embodiment.
And then, based on concentration, the concentration of elemental sulfur B, the concentration of aliphatic hydrocarbon D, the concentration of ammonium thiocyanate C of the extract A of gained, obtain the concentration (step G) of the reduction of the picric acid before based on the conversion of percentage extraction resultant F according to following calculating formula.
(concentration based on the picric acid reduction resultant F before the conversion of percentage extraction)=(concentration of extract A)-(concentration of elemental sulfur B)-(concentration of aliphatic hydrocarbon D)-(concentration of ammonium thiocyanate C)
On the other hand, based in above-mentioned steps A (step S13) UV absorbance analyze result and above-mentioned steps C (step S17) in UV absorbance analyze result, obtain in organism picric acid reduction resultant percentage extraction (step F).
Concrete, the percentage extraction of the picric acid reduction resultant in organism is obtained according to following formula.
(percentage extraction (%))=(1-((absorbancy after extraction)/(absorbancy before extraction))) × 100
And then the percentage extraction that the concentration of the picric acid reduction resultant F before the percentage extraction finally obtained according to above-mentioned steps G converts and above-mentioned steps F obtain, obtains the concentration (step H) of picric acid reduction resultant.
(concentration of picric acid reduction resultant)=(concentration of the picric acid reduction resultant F before percentage extraction conversion) × (100/ (percentage extraction (%)))
Fig. 5 is the figure of an example of the absorption spectrum obtained in the ultraviolet radiation absorption analysis (step C, step S17) after the absorption spectrum and Solid-Phase Extraction obtained in the ultraviolet radiation absorption analysis (steps A, step S13) before display Solid-Phase Extraction.The present inventor finds, as shown in Figure 5, it is relevant that the absorbancy becoming peak near 475nm and picric acid reduce the concentration of resultant.As shown in Figure 5, even if after Solid-Phase Extraction, still remaining at 475nm place have peak.This is because in Solid-Phase Extraction, the part in picric acid reduction resultant residues in aqueous phase.
Thus, the measuring method of the picric acid concentration in the absorption liquid according to the present embodiment, can obtain carrying out percentage extraction conversion, extract organic step in (step B, step S14 ~ step S16) and consider (remaining in aqueous phase) picric acid reduction resultant be not extracted, the concentration of the resultant of picric acid reduction more accurately.
And then, based on the concentration of the picric acid reduction resultant that the measuring method by above-mentioned picric acid concentration measures, adjust the picric amount of adding from catalyzer interpolation pipe S2 (with reference to Fig. 1).Concrete, such as decide picric acid addition based on following formula.
(picric acid addition)=(concentration of the picric acid reduction resultant of mensuration) × (amount of the doctor solution of discharge)
So, in the sulfur method of present embodiment, its addition is adjusted owing to using the concentration self of picric acid reduction resultant, can prevent picric surplus interpolation or addition from tailing off in coke oven gas desulfurization equipment 10, the concentration of the picric acid reduction resultant in absorption liquid can be adjusted in desired pre-determined range.Its result, can suppress the sulphur in thionizer 12 to generate, can contribute to the steady running of thionizer.
In the above-described embodiment, following situation is illustrated, that is: carry out steps A UV absorbance analysis and the step C organism to extraction is carried out for the absorption liquid of discharging to carry out UV absorbance analysis, to obtain the percentage extraction (step F) of the picric acid reduction resultant in organism, try to achieve the picric acid reduction resultant concentration considering this percentage extraction.But the present invention is not limited to this, such as, also can be do not carry out steps A, step C and step F, and reduce resultant concentration based on the picric acid that the result of ultimate analysis and the result of infrared spectroscopic analysis are tried to achieve in absorption liquid.
The method is the picric acid reduction resultant concentration that picric acid reduction resultant concentration before percentage extraction being converted is estimated as in desulfurization system.
In above-mentioned embodiment, the situation using the absorbancy at 475nm place to be extracted rate is illustrated.But, in step F of the present invention, as long as the result based on the UV absorbance analysis (step C) after the result of the UV absorbance analysis (steps A) before organic substance extraction and organic substance extraction obtains the percentage extraction of the picric acid reduction resultant in organism, be not limited to this example.In step F of the present invention, the integrated value of the absorbancy of the pre-determined range interior (such as 400 ~ 500nm) such as comprising 475nm also can be used to calculate percentage extraction.Even this is because comprise the absorbancy in the certain limit of 475nm, the concentration of resultant of also reducing to picric acid is relevant.Concrete, UV absorbance analysis is carried out to the absorption liquid of sampling, obtain the integrated value (steps A) of the absorbancy of the certain limit interior (such as 400 ~ 500nm) comprising 475nm, UV absorbance analysis is carried out for the absorption liquid after extraction organism, obtain the integrated value (step C) of the absorbancy of the certain limit interior (such as 400 ~ 500nm) comprising 475nm, based on the integrated value in above-mentioned steps A and the integrated value in above-mentioned steps C, the percentage extraction (step F) of the picric acid reduction resultant in organism can be obtained.
Embodiment
Use embodiment to be described in detail for the present invention below, but in the scope not exceeding main idea of the present invention, the invention is not restricted to following embodiment.
First, use following reference example 1 so that the measuring method of the concentration of the picric acid reduction resultant before percentage extraction conversion to be described.
(reference example 1)
In the regenerator column 14 shown in Fig. 1, the absorption liquid (doctor solution) of stopple coupon S3 to regeneration arranged from the pipe arrangement 16 carried to thionizer 12 samples, and is extracted thing A through extraction process as shown in Figure 2.In solid-phase extraction column, use the goods name " Sep-PakPlusCSP800 (weighting agent: polystyrene resin, particle diameter: 75 ~ 150 μm) " of Japanese ウ オ mono-タ mono-ズ Co., Ltd..Weigh extract A, obtain the concentration of the extract A in doctor solution.Result is shown in " F-1 (entrance) " hurdle of table 1.
Table 1
The amount (mg/L) of Solid-Phase Extraction thing
The quantitative > of the concentration (mg/L) of < aliphatic hydrocarbon D
Use Fourier transform infrared spectrophotometer (Japan Spectroscopy Corporation's system, goods name " FT/IR410 "), based on the dosing process of the aliphatic hydrocarbon shown in Fig. 3, obtain infrared absorption spectrum.The addition changing octadecane carries out the mensuration of 4 infrared absorption spectrums.In each mensuration, the addition of octadecane is respectively 0.00017mmol, 0.00051mmol, 0.00085mmol and 0.0017mmol.Result as shown in Figure 6.
Fig. 6 is the infrared absorption spectrum that display with the addition of the extract of octadecane.
As shown in Figure 6, two larger absorption spectrums are observed by the extract that with the addition of octadecane.One of them is at frequency 2900cm
-1the neighbouring absorption spectrum being derived from the CH key of aliphatic hydrocarbon D with two peaks.Another is at frequency 2050cm
-1near to observe, absorption spectrum (hereinafter also referred to " spectrum of CN triple bond ") the equitant spectrum of the absorption spectrum (hereinafter also referred to as " spectrum of CN double bond ") being derived from the CN double bond of ammonium thiocyanate and the CN triple bond being derived from internal standard material.Here, the result that the present inventor extensively studies, obtain such discovery: if the area of the spectrum in the region less than the position frequency of the paddy formed between the spectrum of CN double bond and the spectrum of CN triple bond to be regarded as the area of the spectrum of CN triple bond, then this area (also referred to as " supposing the area of CN triple bond spectrum ") is very approximate with the area of the spectrum of actual CN triple bond oneself.In the present embodiment, use the area of this hypothesis CN triple bond spectrum, the area ratio ((area of CH key)/(area of CN triple bond)) of the absorption spectrum obtaining the CH key being derived from aliphatic hydrocarbon D and the absorption spectrum of the CN triple bond that is derived from internal standard material.And, with the addition of octadecane be x-axis (transverse axis), with the area ratio obtained for y-axis (longitudinal axis), carry out linear-apporximation by minimum 2 multiplication, make typical curve.The typical curve made as shown in Figure 7.
Fig. 7 is for the quantitative typical curve of aliphatic hydrocarbon.
The relational expression of y=1990x+7.48 is drawn by above-mentioned typical curve.In this relational expression, bring y=0 into, show that the amount of aliphatic hydrocarbon D is 0.00376mmol/g-KBr by this absolute value.Here, the tablet used during FT-IR measures, be made up of the mixing of extract A:10mg and KBr:1g, therefore, the amount of the aliphatic hydrocarbon D in extract A is 0.376mmol/g-extract.And the molecular weight due to octadecane is 254.49, the amount of the aliphatic hydrocarbon D in extract A is 0.0957g/g-extract.Because the amount of extract A is 327mg/L, the amount of the aliphatic hydrocarbon D in doctor solution is 327 × 0.0957=31mg/L.As mentioned above, the concentration of the aliphatic hydrocarbon D in doctor solution is obtained.
The quantitative > of the concentration (mg/L) of < ammonium thiocyanate C
Use Fourier transform infrared spectrophotometer (Japan Spectroscopy Corporation's system, goods name " FT/IR410 "), based on the dosing process of ammonium thiocyanate shown in Fig. 4, obtain infrared absorption spectrum.Change the addition of ammonium thiocyanate, carry out the mensuration of 4 infrared absorption spectrums, the addition of the ammonium thiocyanate in each mensuration is respectively 0.00034mmol, 0.0010mmol, 0.0017mmol and 0.0034mmol.Result as shown in Figure 8.
Fig. 8 is the figure that display with the addition of the infrared absorption spectrum of the extract of ammonium thiocyanate.
From the extract that with the addition of ammonium thiocyanate, with Fig. 6 the extract that with the addition of octadecane in the same manner as, also observe two larger 2 absorption spectrums.The frequency 2050cm shown wherein is only amplified in Fig. 8
-1neighbouring peak.
As shown in Figure 8, at frequency 2050cm
-1near the absorption spectrum that observes there are 3 peaks, be the equitant spectrum of spectrum of the spectrum of the CN double bond of ammonium thiocyanate and the CN triple bond of internal standard material.Here, the result that the present inventor extensively studies, obtain such discovery: in 3 peaks, the area of the spectrum in region larger for the frequency of the paddy formed between the peak of the side larger relative to frequency and the peak of centre is considered as the area of the spectrum of CN double bond, the area of the spectrum in the region less relative to the frequency of the paddy formed between the peak of centre and the peak of the less side of frequency is considered as the area of the spectrum of CN triple bond, then the ratio of two areas and the absorption spectrum of actual CN double bond oneself and actual CN triple bond oneself absorption spectrum area ratio very approximate.In the present embodiment, obtained the area ratio of the absorption spectrum of CN double bond and the absorption spectrum of CN triple bond by the method.And then, with the addition of ammonium thiocyanate be x-axis (transverse axis), the area ratio obtained is y-axis (longitudinal axis), carry out linear-apporximation by minimum 2 multiplication, make typical curve.The typical curve made as shown in Figure 9.
Fig. 9 is the typical curve for quantitative ammonium thiocyanate.
The relational expression of y=124x+0.394 is obtained by above-mentioned typical curve.In this relational expression, bring y=0 into, the amount thoroughly deserving ammonium thiocyanate C by this is 0.00318mmol/g-KBr.Here, the tablet that FT-IR uses in measuring is made up of the mixing of extract A10mg and KBr1g, and therefore, the amount of the ammonium thiocyanate C in extract A is 0.318mmol/g-extract.And the molecular weight due to ammonium thiocyanate is 76.12, the amount of the ammonium thiocyanate C in extract A is 0.0242g/g-extract.Amount due to extract A is 327mg/L, then the concentration of the ammonium thiocyanate C in doctor solution is 327 × 0.0242=8mg/L.As mentioned above, the concentration of the ammonium thiocyanate C in doctor solution is obtained.
< ultimate analysis >
Use Atomic Absorption SpectrophotometerICP (goods name " PerkinElmer2400SeriesIICHNS/OAnalyzer ", パ mono-キ Application エ Le マ mono-ジ ヤ パ Application Co., Ltd. system), carry out the ultimate analysis of extract A.Result is as shown in " F-1 (entrance) " hurdle of table 2.
Table 2
The ultimate analysis of Solid-Phase Extraction thing
The result of ultimate analysis, the amount as the sulphur of element is 14.3 % by weight.Here, as the sulphur of element, be not only elemental sulfur, also comprise the part forming ammonium thiocyanate.Here, the concentration of elemental sulfur is obtained by following formula.
(concentration of elemental sulfur)=(concentration of extract) × (wt% by the S of ultimate analysis gained)-(concentration of the sulphur in ammonium thiocyanate)
Here, (concentration of the sulphur in ammonium thiocyanate) is obtained by (concentration of ammonium thiocyanate) × ((molecular weight of sulphur)/(molecular weight of ammonium thiocyanate)).
Because the concentration obtaining ammonium thiocyanate is 8mg/L, then (mg/L) × 0.42, (concentration of the sulphur in ammonium thiocyanate)=8 is 3.36mg/L.
Thus (concentration of elemental sulfur)=327 (mg/L) × 14.3%-3.36 (mg/L), the concentration of elemental sulfur is 43mg.
And then, based on concentration, the concentration of elemental sulfur B, the concentration of aliphatic hydrocarbon D, the concentration of ammonium thiocyanate C of the extract A of gained, obtained the concentration of picric acid reduction resultant F by following calculating formula.
(concentration of picric acid reduction resultant F)=(concentration of extract A)-(concentration of elemental sulfur B)-(concentration of aliphatic hydrocarbon D)-(concentration of ammonium thiocyanate C)
The concentration of as above calculated each composition is summarized, as shown in " F-1 (entrance) " hurdle of following table 3.
Table 3
Composition analysis in Solid-Phase Extraction thing
(embodiment 1)
Change the date, from stopple coupon S3, absorption liquid is sampled, by the method same with reference example 1, measure the concentration of the picric acid reduction resultant before percentage extraction conversion.Result is as shown in table 4.In addition, the measurement result of the absorbancy at the 475nm place of the test portion after the absorbancy at the 475nm place of the test portion before organic substance extraction and organic substance extraction is also shown in table 4.In mensuration, use the U-2900 (ultraviolet-visible pectrophotometer) of Co., Ltd. Hitachi Ha イ テ Network ノ ロ ジ mono-ズ.In addition, percentage extraction (%) is also shown in table 4.Percentage extraction (%) is by following formula gained.
(percentage extraction (%))=(1-((absorbancy after extraction)/(absorbancy before extraction))) × 100
In addition, in table 4, also show the concentration of the picric acid reduction resultant after percentage extraction conversion.The concentration of the picric acid reduction resultant after percentage extraction converts is by following formula gained.
(concentration of picric acid reduction resultant)=(concentration of the picric acid reduction resultant F before percentage extraction conversion) × (100/ (percentage extraction (%)))
(embodiment 2 ~ 9)
Change the date, by method similarly to Example 1, measure the concentration of the picric acid reduction resultant before percentage extraction conversion.Result is shown in table 4.In addition, the measurement result of the absorbancy at the 475nm place of the test portion after the absorbancy at the 475nm place of the test portion before organic substance extraction and organic substance extraction is shown in table 4.In addition, also show the concentration of the picric acid reduction resultant after percentage extraction (%), percentage extraction conversion in table 4.The concentration of the picric acid reduction resultant after percentage extraction (%) and percentage extraction convert is obtained similarly to Example 1.
Table 4
Figure 10 is the figure of the curve of the relation shown between the concentration (concentration of the picric acid reduction resultant after percentage extraction conversion) of the picric acid reduction resultant measured in embodiment 1 ~ 9 and the picric acid amount of interpolation.
Figure 11 is the figure of the curve of the picric acid reduction concentration of resultant before the percentage extraction measured in display embodiment 1 ~ 9 converts and the relation between the picric acid amount of interpolation.
Can confirm, the picric acid reduction concentration of resultant after percentage extraction converts and the dependency (with reference to Figure 10) between the picric acid of interpolation are that relevant (the reference Figure 11) reduced between the concentration of resultant and the picric acid of interpolation than the picric acid before percentage extraction converts is correlated with better.It can thus be appreciated that the deviation of the measurement result of the concentration of the picric acid reduction resultant after percentage extraction converts is less.
In addition, for embodiment 1 ~ 9, by this time interim desulfurization system in picric amount, the amount of the doctor solution of discharging outside desulfurization system and the picric amount that is discharged to outside desulfurization system of adding, reduce resultant concentration with the picric acid after percentage extraction converts and be shown in table 5. simultaneously
It should be noted that, be discharged to the picric amount outside desulfurization system, obtained by following formula.
(being discharged to the picric amount (kg/ days) outside desulfurization system)=(picric acid reduction resultant concentration (mg/L)/1000 after percentage extraction conversion) × (discharge the amount (m of the doctor solution outside desulfurization system
3/ hour) × 24)
Table 5
To be display to draw the figure of the relation curve obtained to add picric amount in desulfurization system to for y-axis to discharge picric acid amount outside desulfurization system for x-axis for embodiment 1 ~ 9 Figure 12.
For embodiment 1 ~ 9, to discharge picric acid amount outside desulfurization system for x-axis, drawing to add picric amount in desulfurization system to for y-axis, obtaining the near linear (y=13.061x-156.29) shown in Figure 12 by using method of least squares.Herein, x, namely discharges the picric amount of desulfurization system, as mentioned above, is expressed from the next.
(being discharged to the picric amount (kg/ days) outside desulfurization system)=(picric acid reduction resultant concentration (mg/L)/1000 after percentage extraction conversion) × (discharge the amount (m of the doctor solution outside desulfurization system
3/ hour) × 24)
In addition, y is the picric amount of adding in desulfurization system.
Herein, x and y is substituted into the above-mentioned near linear obtained and is out of shape, then as follows.
(picric acid reduction resultant concentration (mg/L)/1000 after percentage extraction conversion)=[((the picric amount (kg/ days)+156.29 of adding in desulfurization system) × 1000)]/[(13.061 × (discharge amount (m of the doctor solution outside desulfurization system
3/ hour)) × 24]
Therefore, in fact, even if do not measure percentage extraction convert after picric acid reduction resultant, by substituting in desulfurization system the picric amount of adding and the amount of discharging the doctor solution outside desulfurization system, the concentration of the reduction of the picric acid after rate conversion resultant can be extracted.
Its result, almost can obtain the presumed value of the concentration in desulfurization system immediately, thus can add the picric acid with this concentration corresponding amount.
Above, embodiments of the present invention and embodiment are illustrated, but the invention is not restricted to above-mentioned example, within the scope of the formation of the present invention of abundance, the design alteration be suitable for can be carried out.
Claims (2)
1. a sulfur method for coke-oven gas, is the sulfur method of the coke-oven gas by the alkaline aqueous solution containing picric acid reduction resultant, coke-oven gas being carried out to desulfurization, it is characterized in that, comprise the following steps:
Absorption liquid is discharged outside desulfurization system by step X-1;
Step X-2 obtains the concentration by the picric acid reduction resultant in the absorption liquid outside above-mentioned steps X-1 discharge desulfurization system;
Step X-3, based on the picric acid reduction resultant concentration calculated by above-mentioned steps X-2 and the amount of absorption liquid of discharging, obtains the amount of the picric acid reduction resultant be expelled to outside desulfurization system;
Step X-4 adds the picric acid of the amount based on empirical rule in desulfurization system;
Step Y with above-mentioned steps X-1, above-mentioned steps X-2, above-mentioned steps X-3 and the above-mentioned steps X-4 picric acid repeated for one group outside the picric amount that repeatedly obtains adding in desulfurization system and discharge system reduce resultant amount between dependency; And
Step Z, based on the amount of the described dependency according to above-mentioned steps Y gained, the picric amount of adding in desulfurization system, the absorption liquid be discharged to outside desulfurization system, tries to achieve the picric acid reduction resultant concentration in desulfurization system,
Described step X-2 comprises the following steps:
Steps A carries out UV absorbance analysis to the absorption liquid of discharging,
Step B from carried out UV absorbance analyze after absorption liquid extraction organism,
Step C carries out UV absorbance analysis to the absorption liquid extracted after organism,
Step D carries out ultimate analysis to extract,
Step e carries out infrared spectroscopic analysis to extract,
Step F based in above-mentioned steps A UV absorbance analyze result and above-mentioned steps C in UV absorbance analyze result, obtain in organism picric acid reduction resultant percentage extraction,
Step G, based on the result of the infrared spectroscopic analysis in the result of the ultimate analysis in above-mentioned steps D and above-mentioned steps E, is extracted the concentration of the reduction of the picric acid before rate conversion resultant,
The percentage extraction that the concentration of the picric acid reduction resultant before step H converts from the percentage extraction that above-mentioned steps G obtains and above-mentioned steps F obtain, obtains the concentration of picric acid reduction resultant.
2. the sulfur method of coke-oven gas according to claim 1, is characterized in that, comprises the steps:
Picric addition is adjusted according to the picric acid reduction resultant concentration in the desulfurization system that described step Z tries to achieve.
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| JP5584018B2 (en) * | 2010-06-08 | 2014-09-03 | 国立大学法人 鹿児島大学 | Method for measuring picric acid concentration in absorbent used for desulfurization of coke oven gas, and method for desulfurizing coke oven gas using the measurement method |
| JP5787402B2 (en) * | 2011-08-30 | 2015-09-30 | 国立大学法人 鹿児島大学 | Method for measuring concentration of picric acid reduction product in absorption liquid used for desulfurization of coke oven gas, and method for desulfurization of coke oven gas using the measurement method |
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