KR101640372B1 - Method for stabilizing acid gas and combustion effluent gas treating apparatus - Google Patents
Method for stabilizing acid gas and combustion effluent gas treating apparatus Download PDFInfo
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Abstract
(PROBLEMS) To provide an acid gas stabilization treatment method and a combustion exhaust gas treatment facility which appropriately control addition amounts of two alkaline agents having different properties to be added to an acid gas.
A combustion exhaust gas treatment facility 10 to which an acid gas stabilization treatment method is applied is provided with a second acid gas measurement device 30b provided in an inflow path 3, a first addition device 42, A first acid gas measurement device 30a provided in the discharge passage 4, and an addition amount control device 50. The first acid gas measurement device 30a, The addition amount control device 50 includes a first addition amount calculation unit 60 that receives the first acid gas concentration signal S0a and outputs a first addition amount signal S21 and a second addition amount calculation unit 60 that outputs a second acid gas concentration signal S0b, And a second addition amount calculating unit 70 for receiving the first addition amount signal S21 and outputting the second addition amount signal S13. The first adding device 42 and the second adding device 44 add the first alkaline solution to the combustion exhaust gas flowing in the inflow passage 3 based on the first addition amount signal S21 and the second addition amount signal S13, And a second alkaline agent are added.
Description
The present invention relates to a method for producing harmful hydrogen chloride (hydrogenated hydrogen), sulfur oxide (sulfur oxide) generated in a combustion facility such as a municipal waste incinerator, an industrial waste incinerator, a generation boiler, a carbonization furnace, The present invention relates to a stabilization treatment method of a combustion exhaust gas containing an acidic gas such as an acidic gas and an exhaust gas treatment facility and more particularly to a stabilization treatment method of a combustion exhaust gas which efficiently controls an addition amount of an alkali agent for treating an acidic gas, Facilities.
Combustion gases generated from the combustion furnace in the combustion facilities in urban waste incinerators, industrial waste incinerators, power generation boilers, carbonization furnaces, and civilian factories contain acidic gases such as harmful hydrogen chloride gas and sulfur oxide gas. In the combustion facility, two alkaline agents with different properties such as calcium hydroxide (calcium hydroxide) and sodium bicarbonate (sodium bicarbonate) are added to the acid gas, and thereafter the alkaline agent is decomposed in a dust collector such as a bag filter (Dust removal), and then discharged from the chimney in a state in which almost no harmful acid gas is contained.
Fly ash collected in the dust collector contains harmful heavy metals such as palladium (Pd) and cadmium (Cd). These harmful heavy metals are stabilized and then buried and disposed at the final disposal site (see, for example, Patent Document 1).
The slaked lime for treating the acidic gas has a property that the reaction rate with the hydrogen chloride gas increases with the concentration of the hydrogen chloride gas (for example, see Non-Patent Document 1), but the reactivity with the acid gas is low, The reactivity is particularly low.
The alkaline agent, which is an alkaline agent for treating acid gas, has a high reactivity with acid gas compared with the slaked lime, and the sodium hydroxide which is subjected to differential processing with 5 to 30 m has particularly high reactivity with acid gas (for example, patent See Document 2). In other words, the baffle can stably treat the acid gas, and the unreacted portion of the acid gas is less. Therefore, even if the concentration of the acid gas fluctuates violently, it is possible to reduce the addition amount of the acidic gas while stably processing the acid gas by adding an appropriate amount of the acidic gas in accordance with the concentration of the acid gas. Therefore, it is possible to reduce the amount of collected fly ash and furthermore, the amount of the landfill. Therefore, adding the sulfuric acid to the acidic gas is an effective means for reducing the environmental load (environmental load).
However, in general, the concentration of the acid gas emitted from combustion furnaces such as industrial waste incinerators and private factories fluctuates violently. Thin lime is economically inexpensive, but its reaction with acid gas is slow and its reaction with sulfur oxides is particularly slow. For this reason, it is difficult to apply only the slaked lime to the acid gas because it is difficult to apply to industrial waste incinerators or civilian factories where the concentration of acid gas fluctuates greatly.
In addition, since the reaction with the acid gas is high and the reaction with the acid gas is fast, the acid gas can be stably treated. However, sodium (Na) is higher than calcium (Ca). For this reason, the method of adding only the sulfuric acid to the acidic gas and stably treating it is particularly economically burdened when applied to an industrial waste incinerator or a private factory where a large amount of acid gas is generated.
An object of the present invention is to provide an acid gas stabilization treatment method and a combustion exhaust gas treatment facility which appropriately control addition amounts of two alkaline agents having different properties to be added to an acidic gas.
The inventors of the present invention found that the addition amount of the first alkali agent is calculated based on the information on the acid gas and the addition amount of the second alkaline agent is calculated on the basis of the information of the addition amount of the first alkaline agent, And found that the above object can be achieved by adding the calculated amount of the alkaline agent to the acid gas, thereby completing the present invention.
The present invention provides the following.
The acid gas stabilization treatment method according to the present invention stably treats a combustion exhaust gas containing an acidic gas in a combustion exhaust gas treatment facility. The stabilization treatment method includes a first acidic gas concentration measuring step of measuring a concentration of the first acidic gas in the treated exhaust gas after treatment of the flue gas discharged from the dust collector and a second acidic gas concentration measuring step of measuring the concentration of the acidic gas A first calculation step of calculating first additive amount information on the basis of the first additive amount information on the basis of the first acid gas information and on the basis of the first additive amount information on the basis of the first acid gas information, A second acidic gas concentration measuring step of measuring a concentration of the second acidic gas in the second acidic gas which is an untreated combustion exhaust gas not treated in the dust collector, and a second acidic gas concentration measuring step of measuring the concentration of the acidic gas A second calculation for calculating the second acid gas information, calculating an addition amount of the second alkali agent based on the second acid gas information, and calculating second addition amount information based on the addition amount, A first adding step of adding the first alkaline agent of the first added amount to the combusted exhaust gas; and a second adding step of adding the second alkaline agent of the second added amount to the combusted exhaust gas.
Wherein the first adding amount information includes a control target value which is a target value of the first acid gas concentration in the post-treatment exhaust gas stream, and the second calculating step includes a step of calculating a concentration by subtracting the control target value from the second acid gas concentration It is preferable to calculate the second addition amount.
Wherein the second acidic gas information includes an acidic gas concentration amount indicating a rate of change of an instantaneous acidic gas concentration which is a real time acidic gas concentration measured in the second acidic gas concentration measuring step, After the normal addition amount of the first alkali agent is calculated on the basis of the first acid gas information, the normal addition amount is corrected on the basis of the predetermined correction method in accordance with the acid gas concentration amount , It is preferable to calculate the first addition amount information .
Wherein the acid gas stabilization treatment method specifies basic addition amount correspondence information that associates the instant acid gas concentration and the addition amount of the first alkaline agent in advance and the first calculation step is a step of determining whether or not the acid gas concentration amount remains constant Or in a decreasing descent state, the normal addition amount is calculated on the basis of the instantaneous acid gas concentration and the base addition amount information for reduction, and in the ascending state in which the acid gas concentration amount is increasing, It is preferable to calculate the normal addition amount on the basis of the basic addition amount corresponding information for increasing the acid gas concentration and the value of the acid gas concentration in the basic addition amount correspondence information by a predetermined correction method.
Wherein the first calculation step is a step of calculating the normal addition amount by a descending correction value in a range exceeding a predetermined value and falling within a range of less than 1 in the case of the descending state in which the acid gas concentration amount is kept constant or decreasing It is preferable to correct it.
A plurality of corresponding additive upper limit values are set between a maximum additive amount and a minimum additive amount that can be added in the first additive step and the plurality of corresponding additive amount upper limit values each correspond to a plurality of acidic gas concentrations, Wherein the gas information includes an instantaneous acid gas concentration which is an acid gas concentration measured in the second acid gas concentration measuring step, and the first calculating step includes a step of calculating the concentration of the instant acid gas, It is preferable to calculate the normal addition amount on the basis of the upper limit value of the corresponding addition amount corresponding to the higher concentration among the two adjacent acid gas concentrations.
Wherein the first acid gas information includes an average acid gas concentration which is an average value of the first acid gas concentration at a predetermined time, and the first calculation step is a step of calculating the average acid gas concentration, , It is preferable to calculate the first addition amount information based on the predetermined emergency addition amount instead of the normal addition amount.
Wherein the second acidic gas includes a hydrogen chloride gas and / or a sulfur oxide gas, and the second acidic gas concentration measuring step includes a hydrogen chloride gas concentration measuring step of measuring the concentration of the hydrogen chloride gas in the second acidic gas and / And a sulfur oxide concentration measuring step of measuring a sulfur oxide concentration in the second acidic gas, wherein the second acidic gas information includes hydrogen chloride information on the hydrogen chloride gas and / or sulfur oxide information on the sulfur oxide gas And the first calculation step calculates the normal addition amount based on the hydrogen chloride gas addition amount calculated on the basis of the hydrogen chloride information and / or the sulfur oxide gas addition amount and / or the basic addition amount calculated on the basis of the sulfur oxide information , And the base addition amount is determined based on the amount of the first addition amount information It is preferably calculated on the basis of the average addition amount.
The addition amount of the first alkaline agent is preferably 0.1 to 0.6 equivalents per acidic gas concentration before the addition of the alkali agent and the addition amount of the second alkaline agent is preferably 0.5 to 3.0 equivalents per acidic gas concentration before the addition of the alkali agent.
The acid gas stabilization treatment method preferably further includes a fixing treatment step of adding at least one selected from an iron-based compound, a phosphoric acid-containing compound and a neutralizing agent to the fly ash collected in the dust collector.
The combustion exhaust gas treatment facility according to the present invention is a facility for executing the acid gas stabilization treatment method described in any one of the above. The combustion exhaust gas treatment facility comprises a dust collector, an inlet passage for introducing the exhaust gas to the dust collector, an exhaust passage for discharging the treated exhaust gas from the dust collector after being treated in the dust collector, A second acid gas measurement device for performing the second acid gas concentration measurement step and outputting the second acid gas concentration measurement signal as a second acid gas information signal; A first adding amount calculating unit for executing the first calculating step on the basis of the acid gas information signal and outputting the first added amount as a first adding amount signal and a second adding amount calculating unit for executing the second calculating step on the basis of the second acid gas information signal And a second additive amount calculating unit that outputs the second additive amount as a second additive amount signal based on the first additive amount signal, And a first adding unit for executing the process on the basis of the second amount signal and a second addition device for performing the second addition step.
According to the present invention, it is possible to provide an acid gas stabilization treatment method and a combustion exhaust gas treatment facility for appropriately controlling addition amounts of two alkaline agents having different properties, which are added to an acid gas.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual diagram showing an acid gas stabilization treatment method and a combustion exhaust gas treatment facility according to the present invention. Fig.
Fig. 2 is a detailed conceptual diagram of a part of the acid gas stabilization treatment method and the combustion exhaust gas treatment facility shown in Fig. 1;
Fig. 3 is a detailed conceptual diagram of the acid gas stabilization processing method shown in Fig. 1 and another part of the combustion exhaust gas processing facility.
Fig. 4 is a graph showing the basic addition amount correspondence information and correction of the acid gas stabilization method and the combustion exhaust gas treatment facility shown in Fig. 1; Fig.
5 is a graph showing the basic addition amount correspondence information of the acid gas stabilization treatment method and the combustion exhaust gas treatment facility shown in FIG. 1, and other corrections thereto.
Fig. 6 is a flowchart for explaining the acid gas stabilization processing method shown in Fig. 1;
Fig. 7 is a flowchart for explaining the acid gas stabilization processing method following Fig. 6;
8 is a graph showing the results of the comparative example.
9 is a graph showing the results of the embodiment.
10 is a time-series graph showing the results of the comparative example.
11 is a time-series graph showing the results of the embodiment.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. Hereinafter, embodiments will be described concretely, but the present invention is not limited thereto.
[Combustion gas processing facility]
As shown in Fig. 1, the combustion exhaust
The combustion exhaust
The combustion exhaust
The combustion exhaust
The first adding
The first alkali agent is added for the purpose of titration of an acidic gas, and therefore there is no particular limitation on its kind, but an alkaline agent having a relatively high reactivity with an acidic gas is preferable. As the first alkali agent, a mean particle size of the finely divided sodium bicarbonate adjusted to 5~30μm (微粉重曹), a specific surface area of 30m 2 / g or more and the reaction of calcium hydroxide and / or their reactivity can be mentioned a mixture, a medicament formulated for high alkaline agent have. Particularly, since the differential boiling tank having an average particle diameter of 5 to 30 占 퐉 exhibits high reactivity with not only hydrogen chloride but also sulfur oxide, it is preferable to apply a differential boiling tank in a facility where treatment with sulfur oxide is required. Further, for example, these alkaline agents such as sulfuric acid may be used by locally grinding an alkaline agent having a large particle size.
The second alkali agent is added for the purpose of roughly eliminating the acidic gas, so that there is no particular limitation on its kind. However, it is economically preferable that an alkaline agent which is relatively low in reactivity with an acidic gas is available. Examples of the second alkaline agent include JIS special lime lime, high-reacting lime having a specific surface area of 30 m 2 / g or more, sodium hydroxide, crude sesame oil, sodium sesquicarbonate, natural soda, Magnesium, magnesium hydroxide, and / or an alkaline agent are mixed and blended. The second alkaline agent may be a slurry or an aqueous solution in which each alkali agent is dissolved in water.
In the case where the second alkali agent is a calcium hydroxide, the second alkali agent is preferably added in an amount of 0.5 to 3 equivalents, preferably 1 to 2 equivalents, per the acid gas concentration (HCl, SO 2 ) generated.
In the case where the first alkaline agent is precipitated in a fine powder, the first alkaline agent is preferably used in an amount of 0.10 to 0.60 equivalents per equivalent of the acid gas concentration (HCl, SO 2 ) generated, so that the first alkaline agent can be stably treated with both hydrogen chloride and sulfur oxide, It is preferable to add it in an amount of 0.15 to 0.50 equivalents.
The first adding
The
The first acid
The second acid
The first and second hydrogen chloride gas
The combustion exhaust
The addition
The first addition amount signal S21 represents the first addition amount (kg / h) per unit time of the first alkaline agent added by the
The addition
Here, in general, the first and second hydrogen chloride gas
The additive
Thus, as described later, the addition
The first addition
The first main additive
The first hydrogen chloride
The first sulfur oxide
As shown in FIG. 2, the first hydrogen chloride
The addition amount
The basic addition amount correspondence information is information indicating the acidic gas concentration corresponding to the lower limit (the minimum addition amount LOS (kg / h)) of the addition
In general PID control, the upper limit value of the control output is only one. For example, when the control target value is set to 40 ppm, for example, when the acid gas concentration exceeds the control target value, The first alkaline agent is added to the upper limit value, resulting in an excessive addition.
On the other hand, the additive amount
For example, as shown in Figs. 4 and 5, the basic addition amount correspondence information is information indicating the addition amount SQ (kg) to be added to the instantaneous hydrogen chloride gas concentration PV of the hydrogen chloride gas concentration signal S1a / h), the line connecting the points 0 - point a - point b, the line connecting point c - point d, and the line after point e.
The addition amount corresponding information line L is specifically as follows. In the range from 0 ppm to the control target value (also referred to as the control output start concentration) (SV) (ppm)) (the range from 0 to the point a), the addition amount SQ ( kg / h) is defined as zero.
The first output limit corresponding concentration SM1 (ppm) corresponding to the first output limit addition amount LM1 (kg / h) and the instantaneous hydrogen chloride gas concentration PV (ppm) (The range from point a to point b), the addition amount SQ (kg / h) is defined based on the following formula.
The addition amount SQ of the first output limit addition amount LM1 × the instantaneous hydrogen chloride gas concentration PV the control target value SV the first output limit correspondence concentration SM1 the control target value SV,
The instantaneous hydrogen chloride gas concentration (PV) (ppm) is equal to or higher than the first output limit corresponding concentration SM1 (ppm) corresponding to the first output limit addition amount LM1 (kg / h) the addition amount SQ (kg / h) is smaller than the second output restricting addition amount LM2 (kg / h) in the range (from the point c to the point d) ) (kg / h).
In the case where the instantaneous hydrogen chloride gas concentration (PV) (ppm) is equal to or higher than the second output limit corresponding concentration SM2 (ppm) corresponding to the second output limit addition amount LM2 (kg / h) The addition amount SQ (kg / h) is defined as the output upper limit addition amount LM3. The output upper limit addition amount LM2 and the output upper limit addition amount LM3 are both the upper limit of the corresponding addition amount.
As shown in Fig. 2, the concentration-
Based on the average addition amount of the first addition amount (kg / h) at a predetermined time such as 10 minutes, for example, the basic addition
The ascending correction
When the value of the hydrogen chloride gas concentration amount [theta] is not changed or is a negative value, that is, when the hydrogen chloride gas concentration is stable or descending, the downward correction correction
The addition
As shown in Fig. 3, the first sulfur oxide
The addition amount
3, the concentration-
Based on the average addition amount of the first addition amount (kg / h) at a predetermined time such as 10 minutes, for example, the basic addition
The ascending correction
When the value of the sulfur oxide gas concentration amount [theta] is not changed or is a negative value, that is, when the sulfur oxide gas concentration is stable or dropping, the fall correction
The addition
The base addition
The base addition amount Fa (kg / h) is an average addition amount (kg / h) of the first addition amount (kg / h) per predetermined time such as 10 minutes, for example.
The normal addition
Generally, PID control is well used for the addition amount control device. And the PID control can be set only to a single upper limit output value and a lower limit output value. Therefore, for example, in a general PID control, when the control target value (ppm) of the hydrogen chloride gas concentration in the
The normal addition
The emergency
Generally, the combustion exhaust gas treatment facility manages the exhaust gas discharged after the treatment by the average concentration (ppm) of the hydrogen chloride gas concentration (ppm) or the sulfur oxide gas concentration (ppm) for one hour.
On the other hand, in the combustion exhaust
Particularly, since reduction of the addition amount (kg / h) of the first alkali agent and stable treatment of the hydrogen chloride gas and the sulfur oxide gas are contradictory to each other, when the addition amount (kg / h) of the first alkali agent is reduced, ppm) is likely to exceed the determined management concentration (ppm).
Therefore, when the emergency
When the urgent-time determination signal S7 indicating normal is received, the added-
That is, when the average value of the acid gas concentration (ppm) exceeds the predetermined emergency addition concentration (ppm), the addition
The device addition
Accordingly, the device addition
The second addition
Control target
The second addition amount
The average second additive
The device addition
The second addition amount (AgCQ) (kg / h) is calculated from the second acid gas concentration (the second hydrogen chloride concentration (inlet HCl) and / or the second sulfur oxide concentration (inlet SOx)) in the untreated combustible- (SV HCl , SV SO2 ) of the first acid gas concentration (the first hydrogen chloride concentration (outlet HCl) and / or the first sulfur oxide concentration (outlet SOx)) set by the feedback control Is calculated based on the concentration. The means for calculating the second addition amount AgCQ (kg / h) by subtracting the control target value SV is an effective means for reducing the addition amount of the second alkaline agent.
That is, the theoretical required amount of the second alkaline agent is determined by subtracting the first hydrogen chloride concentration (the outlet HCl) from the second hydrogen chloride concentration (inlet HCl) and / or by subtracting the first sulfur oxide concentration (AgCQ) (kg / h) calculated on the basis of the concentration obtained by subtracting the concentration of SOx from the concentration of SOx.
Conventionally, the second alkali agent is added in proportion to the second hydrogen chloride concentration (inlet HCl) and the second sulfur oxide concentration (inlet SOx), but the first hydrogen chloride concentration (outlet HCl) and the first sulfur oxide concentration The loss was caused by the fluctuation of the second hydrogen chloride concentration (inlet HCl) and the second sulfur oxide concentration (inlet SOx). On the other hand, the control target value SV of the first alkaline agent serving as the index of the first hydrogen chloride concentration (outlet HCl) and the first sulfur oxide concentration (outlet SOx) is set as the second hydrogen chloride concentration (inlet HCl) and the second sulfur oxide concentration The addition amount of the second alkaline agent can be controlled in proportion to the theoretical addition amount, and the second alkaline agent can be added efficiently by calculating the second addition amount (AgCQ) (kg / h) based on the concentration obtained by subtracting . It is also appropriate to calculate the theoretical required amount in accordance with the measured values of the first and second hydrogen chloride concentrations and the first and second sulfur oxide concentrations. The control target value SV is controlled by, for example, an oxygen conversion value It is preferable to perform the subtraction in terms of the measured value.
The first adding
The
Specifically, the heavy metals contained in the fly ash are generally immobilized (immobilized) by the addition of a chelate such as diethyldithiocarbamate to be insolubilized. However, the fixation effect by the chelate of heavy metals is high in the short term, but there is a possibility that the pH is lowered due to the acid rain at the final disposal site and the heavy metals such as lead are re-eluted from the heavy metals immobilized by oxidative magnetization of the chelate.
Therefore, by adding a phosphate compound such as phosphoric acid to heavy metals, it is possible to change the added heavy metals to the form of hydroxyapatite, which is an inorganic mineral, so that the long-term stability at the final disposal site is excellent. Therefore, the stabilization treatment of adding phosphoric acid and other phosphoric acid compounds to heavy metals is a highly valuable treatment method from the viewpoint of environmental protection. In addition, the method of treating fly ash with a heavy metal fixing agent such as phosphoric acid is an effective means for reducing environmental load.
The heavy metal fixing agent for fixing the heavy metal contained in the fly ash can be applied to fly ash without any particular limitation, and it is sufficient that the fixing effect of heavy metal can be obtained. As the heavy metal fixing agent, an organic chelating agent is generally used. Examples of the organic chelating agent include piperazine dithiocarbamate, diethyldithiocarbamate, dimethyldithiocarbamate, dibutyldithiocarbamate, and the like. For example.
From the viewpoint of long-term immobilization of heavy metals in the disposal step, heavy metal immobilization by a phosphate compound which forms chloropyromorphite and fixes it in the form of mineral is an effective means. As the phosphoric acid compound, the phosphoric acid or the phosphate may be a water-soluble phosphoric acid compound and may be in the form of a powder or an aqueous solution, and examples thereof include polyphosphoric acid (orthophosphoric acid), polyphosphoric acid, metaphosphoric acid, polyphosphoric acid, , Sodium pyrophosphate, sodium pyrophosphate, sodium pyrophosphate, sodium secondary phosphate, sodium tertiary phosphate, potassium primary phosphate, potassium secondary phosphate, potassium tertiary phosphate, calcium primary phosphate, calcium secondary phosphate, magnesium primary phosphate , Magnesium phosphate monobasic, ammonium phosphate dibasic, ammonium dibasic, lime super phosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium pyrophosphate, sodium pyrophosphate, potassium phosphite , Sodium hypophosphite, potassium hypophosphite, and the like. Especially, Pure phosphoric acid, monophosphate, diphosphate, tribophosphate, tripolyphosphate, hexametaphosphate and pyrophosphate show good heavy metal fixing effect. In addition, it is preferable to mix an aqueous solution of phosphate or an alkaline agent such as sodium hydroxide to adjust the pH to 3 or more, because there is a risk of corrosion to the piping.
In addition, the elution of lead can be prevented by the silicon dioxide-containing compound. The silicon dioxide-containing compound may be silicon dioxide itself, or may be a mixture or composite of silicon dioxide and another material if the silicon dioxide is soluble. The silicon dioxide may be in the form of a powder or a liquid. Silicon dioxide of the powder includes silica fume, silica gel, activated clay (active white), zeolite and the like. The liquid silicon dioxide may be an aqueous solution of sodium silicate (water glass) or an aqueous solution of potassium silicate.
Further, it is preferable to add an iron-based compound in addition to these agents so that hexavalent chromium, arsenic, selenium, mercury, etc. do not elute from the heavy metal. Examples of the iron-based compound include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, ferrous sulfate and iron powder. Ferrous chloride is most preferred.
Furthermore, when the fly ash contains many alkali residues, it is preferable to use a neutralizing agent such as inexpensive aluminum chloride, polychlorinated aluminum, hydrochloric acid, and sulfuric acid alumina together with an alkaline agent.
When solidification treatment of fly ash is carried out, it is possible to use calcined gypsum, portland cement, rapid hardening cement, jet cement, blast furnace cement, alumina cement cement such as alumina cement may be added.
Particularly, when heavy metal treatment is carried out by applying at least one iron-based compound, a phosphoric acid compound, a neutralizing agent and a silica-containing compound to heavy metals in fly ash, unreacted alkali residues increase the addition amount of these heavy metal fixing agents. On the contrary, by applying the stabilization treatment method of the present invention, it is possible to optimize the addition amount of the alkali agent, reduce the unreacted alkali residual, reduce the addition amount of the fly ash heavy metal fixing agent, and reduce the environmental load .
It is also preferable to measure the amount of the alkali residue in the fly ash and measure the amount of the additive in accordance with the value of the measured amount of the alkali residue with a means for specifying the amount of the acidic agent such as the neutralizing agent or phosphoric acid of the fly ash. As a result, an acidic agent such as a neutralizing agent or phosphoric acid can be added or not added in an insufficient manner, and appropriate use and stable treatment of the drug can be realized.
[Acidic gas stabilization treatment method]
An acid gas stabilization treatment method executed by the combustion exhaust gas treatment facility (10) will be described.
≪ Calculation of first additive amount >
First, during operation of the combustion exhaust
Specifically, the first hydrogen chloride gas
The first hydrogen chloride
6, the base addition
Next, the addition
4, the additive
Specifically, the addition
Next, the additive
6, the addition
First, when the instantaneous hydrogen chloride gas concentration PV is in the range from 0 to the "control target value SV (ppm) -incremental correction value SVA (ppm)" (step ST05 , And the addition amount SQ (kg / h) is calculated as 0 based on the addition amount corresponding information line L2 (step ST07).
Further, the addition
Specifically, in the addition amount corresponding information line L2, the first output limitation corresponding concentration SM1 (ppm) - the rising correction value SVA (ppm) is calculated from the "control target value SV ) (ppm) "of the additive amount SQ (kg / h) is calculated based on the following formula.
The addition amount SQ = the first output limited addition amount LM1-the basic addition amount Fa 占 the instantaneous hydrogen chloride gas concentration PV - the control target SV-the first correction value SVA / Limit correspondence concentration (SM1) - Control target value (SV)]
The addition
Addition amount (SQ) = output upper limit addition amount (LM2) -base addition amount (Fa)
When the instantaneous hydrogen chloride gas concentration PV exceeds the "second output limit correspondence concentration SM2 (ppm) -incremental correction value SVA (ppm)" (step ST13 , And the addition amount SQ (kg / h) is calculated based on the addition amount corresponding information line L2 (step ST17). At this time, the addition amount SQ (kg / h) in a range exceeding the "second output limit correspondence concentration (SM2) (ppm) - the upward correction value SVA (ppm) . ≪ / RTI >
Addition amount (SQ) = output upper limit addition amount (LM3) -base addition amount (Fa)
7, the addition
5, the additive
Specifically, the addition
7, the addition
First, when determining that the instantaneous hydrogen chloride gas concentration PV is in the range from 0 to the "control target value SV (ppm)" (step ST19), the addition
If the addition
Specifically, the addition amount SQ (kg / h) in the range from the "control target value SV (ppm)" to the "first output limit correspondence concentration SM1 (ppm)" of the addition amount corresponding information line L4 is expressed by the following equation .
The addition amount SQ = the first output limitation addition amount LM1 x the descending correction coefficient LMG base addition amount Fa x the instantaneous hydrogen chloride gas concentration control target value SV / Corresponding concentration (SM1) - control target value (SV)]
The addition
Addition amount (SQ) = Output upper limit addition amount (LM2) × Reduction correction coefficient (LMG) - Base addition amount (Fa)
When the instantaneous hydrogen chloride gas concentration PV exceeds the second output limit corresponding concentration SM2 (ppm) (step ST27), the additive
Addition amount (SQ) = Output upper limit addition amount (LM3) × Reduction correction coefficient (LMG) - Base addition amount (Fa)
In this way, the addition
The first sulfur oxide
The basic addition
The normal addition
(Kg / h) = addition amount of hydrogen chloride side (AgS1) (kg / h) + sulfur oxide side addition amount (AgS2) (kg / h) + basic addition amount (Fa)
The
When the urgent-time determination signal S7 indicating normal is received, the added-
The device addition
≪ Calculation of second addition amount >
During the operation of the combustion exhaust
Specifically, the second hydrogen chloride gas
Although the second hydrogen chloride gas concentration signal S1b and the sulfur oxide gas concentration signal S2b are outputted here, the output may be any one of them.
The second additive amount
The average second addition
The apparatus addition
≪ Addition of alkaline agent &
The first adding
According to the above-mentioned combustion exhaust
[Example]
Although the present invention will be described in more detail with reference to the following examples, the flue
<Comparative Example>
The second hydrogen chloride gas
At this time, the feedback control by the first hydrogen chloride gas concentration signal S1a and the first sulfur oxide gas concentration signal S2a of the differential alkaline solution (first alkaline agent) was carried out by the setting shown below.
In addition, the fly ash in the present application method was periodically sampled and the raw material INDEX (alkali residue) serving as an index of unreacted components of the alkali agent was measured. In addition, an elution test of heavy metals (Test No. 13 of Japan Environment Agency) was carried out by adding an aqueous solution of sulfuric acid alum and phosphoric acid, and the required addition amount was evaluated.
Under this evaluation condition, the first hydrogen chloride gas concentration (outlet HCl) was adjusted to 195 ppm (control target value of 200 ppm) by adding 1.88 equivalent (338 kg / h) of slaked lime and 0.28 equivalent (115 kg / It was possible to carry out the control, and proper control was possible.
Figs. 8 and 10 show the transition of the second hydrogen chloride gas concentration (inlet HCl) and the addition amount of slaked lime.
According to the graph of Fig. 8, the amount of hydrated lime added tends to decrease as the second hydrogen chloride gas concentration (inlet HCl) increases. This is because when the second hydrogen chloride gas concentration (inlet HCl) is low, the slaked lime is excessively sprayed, and when the second hydrogen chloride gas concentration (inlet HCl) is lowered, the slaked lime is insufficient and the addition amount of the relatively expensive first alkali agent is increased .
Regarding heavy metal treatment of fly ash, the average of the raw material INDEX (alkali residual) in fly ash was 305. Further, 3% of 75% phosphoric acid aqueous solution was added, and the necessary amount of 27% aluminum sulfate aqueous solution was changed by changing the addition amount of 27% aluminum sulfate aqueous solution.
<Setting of control>
Second alkali agent: Calcium lime: 338 (kg / h) Quantitative addition
First alkaline agent: Feedback control of the differential salt bath
AgSO = AgSQ /
AgSO: Output power (%)
AgSQ: Addition amount of fine powder (normal addition amount) (kg / h)
LHS: the maximum addition amount of the differential bead addition apparatus (the maximum addition amount of the first addition apparatus) (kg / h)
AgSQ = (AgS1 + AgS2) + Fa
AgS1: Addition amount (addition amount of hydrochloric acid side) (kg / h) specified from output of outlet HCl measuring device
AgS2: Addition amount (sulfur oxide added amount) (kg / h) specified from the output of the outlet SOx measuring device
Fa: Base addition amount (kg / h) = n min. Moving average addition amount (kg / h) x coefficient (%) ÷ 100
n minutes Moving average: 10 (minutes)
Coefficient: 70.0 (%)
Here, when the AgSQ exceeds the LHS, the LHS is set.
Also, when AgSQ is equal to or less than LOS (the minimum addition amount of the first additive device) (kg / h) or less, the LOS was used.
LOS: Minimal addition amount of the additive for mineral base addition (minimum addition amount of the first addition device): 40 kg / h
In addition, when the outlet HCl concentration (hydrogen chloride gas concentration) and the outlet SOx concentration (sulfur oxide gas concentration) become equal to or more than a predetermined concentration, addition output of the emergency addition amount is specified separately from this addition output.
Emergency dose
Emergency addition [control by 1 hour average of outlet HCl]
HCl Emergency addition concentration: 213 (ppm)
HCl Emergency addition level: 260 (kg / h)
Emergency addition [control by outlet time SO2 1 hour average]
SO2 Emergency addition concentration: 200 (ppm)
SO2 Emergency class: 260 (kg / h)
Table 1 and Table 2 show control settings.
[Table 1] Exit HCl feedback control AgS1
[Table 2] Exit SO 2 feedback control AgS2
<Examples>
The same procedure as in the comparative example was carried out except that the necessary amount of slaked lime (the second alkali agent, JIS special lime slag) was calculated and added in the same facility based on the second hydrogen chloride gas concentration signal S1b.
Control of the slaked lime (second alkaline agent) and the differential alkaline agent (first alkaline agent) was carried out by the control setting shown below.
The fly ash in this application method is also regularly sampled and the average of the raw material INDEX (alkali residue) which is an indicator of the unreacted components of the alkali agent as in the comparative example is measured, The required amount of addition was evaluated using an aqueous solution of phosphoric acid.
The first hydrogen chloride gas concentration (the outlet HCl) was increased by adding 1.67 equivalents (278 kg / h) of slaked lime and 0.27 equivalents (104 kg / h) of the differential precipitation to the conditions under which the addition amount of the slaked lime was controlled by the addition amount of the differential liquor 196ppm (control target value 200ppm), and proper control was possible. Further, by controlling the slaked lime according to the present invention, the required addition amount of the slaked lime can be greatly reduced as compared with the comparative example.
9 and 11 show the transition of the second hydrogen chloride gas concentration (inlet HCl) and the addition amount of slaked lime, the present control shows that the addition of slaked lime to the stable equivalent of the second hydrogen chloride gas concentration (inlet HCl) This is a highly controllable control.
Regarding the heavy metal treatment of fly ash, the average of the INDEX (alkali residual) of fly ash in the fly ash was 225, which was lower than that of the comparative example. In addition, due to the improvement in controllability, the fluctuation was reduced, and the product became scattered ash which is easy to be treated with an acidic medicament.
Similarly, when 3% of 75% aqueous phosphoric acid solution was added and the amount of 27% aqueous aluminum sulfate solution was changed to evaluate the required amount of addition, the required amount of 27% aqueous aluminum sulfate solution was 40% on average, there was.
≪ Control of first alkaline agent &
The control of the first alkaline agent (differential dyeing) was the same as that in the comparative example.
≪ Control of the Second Alkali Agent >
AgCO = AgCQ /
AgCO: Calcined addition power (%)
AgCQ: Amount of lime added (kg / h)
LHC: Maximum addition amount of slaked lime addition apparatus (maximum addition amount of the second addition apparatus): 450 (kg / h)
100? Mc? 1000? AgCQ = A? 100 占
A: total adjustment factor
B: inlet HCl adjustment factor
Inlet HCl: inlet HCl concentration (ppm) [found]
SV HCl : Control target value (ppm) of the outlet HCl in the control of the first alkaline agent [measured value]
When the outlet HCl concentration signal is an oxygen conversion value, it is converted into a measured value and calculated by the following equation.
SV HCl [measured value] = SV HCl [in terms of oxygen] × 21 - oxygen concentration (%) ÷ (21-12)
F: Amount of exhaust gas (Nm3 - wet / h)
W: Moisture content in gas (%)
Mc: Pharmaceutical Coefficient (Lime): 37
LMHC: Maximum amount of slime control
LMOC: Lime scale control minimum addition amount
Here, when AgCQ exceeds LMHC, it is determined as LMHC.
When AgCQ is equal to or less than LMOC, LMOC is used.
Control of secondary alkaline agent (slaked lime)
LOC: Minor additive amount of slaked lime: 45 (kg / h)
LHC: Maximum amount of added lime equipment (kg / h): 450 (kg / h)
LMOC: Calcined Lime Control Minimum Addition: 45 (kg / h)
LMHC: Maximum amount of slime control added: 405 (kg / h)
A: Overall adjustment factor: 200 (%)
B: inlet HCl adjustment factor: 100 (%)
The acid gas treatment results are shown in Table 3, and the heavy metal treatment results are shown in Table 4 as the measurement results.
[Table 3] Comparative Example, Example, Result of Acidic Gas Treatment
[Table 4] Comparative Example, Example, Heavy Metal Treatment Result
AgCQ - second addition amount; AgCQA - average second addition amount;
AgS1 - hydrogen chloride added amount; AgS2 - Sulfur oxide side addition amount;
AgSQ - first added amount, usually added amount; AgSQA - average first addition amount;
AgSQT - target addition; Fa - base addition;
L, L1, L2, L3, L4 - additive amount corresponding information line; LHS - maximum addition amount;
LM1 - first output limit addition amount; LM2 - output upper limit additive amount;
LM2 - second output limit addition amount; LM3 - output upper limit additive amount;
LMG - Downward Correction Factor; LOS - minimum addition;
PV - instantaneous hydrogen chloride gas concentration, instantaneous sulfur oxide gas concentration;
S0a - first acid gas concentration signal; S0b - second acid gas concentration signal;
S1a - the first hydrogen chloride gas concentration signal; S1b - second hydrogen chloride gas concentration signal;
S2a - the first sulfur oxide gas concentration signal; S2b - second sulfur oxide gas concentration signal;
S3 - hydrogen chloride addition signal; S4 - Sulfur oxide addition signal;
S5 - Base additive signal; S6 - normal additive amount signal; S7 - emergency signal;
S8 - Additive amount signal of gauze 1; S11 - average first addition amount signal;
S12 - an average second addition amount signal; S13 - second addition amount signal;
S14 - the exit control target value signal; S21 - the first addition amount signal;
S22 -
SM2 - second output limit corresponding concentration; SQ - Additive amount; SV - control target value;
SV - target value; SVA - rising correction value; 2 - piping; 3 - inflow path;
4 - discharge path; 10 - Combustion gas treatment facility; 12 - combustion furnace; 14 - Boilers;
16 - Sense Tower; 18 - dust collector; 19 - fly ash kneader; 20 - Fan; 22 - chimneys;
30a - a first acid gas measuring device; 30b - a second acid gas measuring device;
32a - a first hydrogen chloride gas concentration measuring device;
32b - a second hydrogen chloride gas concentration measuring device;
34a - a first sulfur oxide gas concentration measuring device;
34b - a second sulfur oxide gas concentration measuring device; 42 - a first addition device;
44 - a second addition device; 50 - Addition amount control device; 60 - a first additive amount calculating unit;
61 - main additive amount calculating unit; 62a - hydrogen chloride gas calculator;
62b - sulfur oxide gas calculator; 63 - base additive amount calculating unit;
64 - a normal additive amount calculating unit; 65- Emergency Case Judge; 66 - an affinity calculation unit;
67 - equipment addition limitations; 70 - a second addition amount calculating unit;
72 - an average second addition amount calculating unit; 73 - limit of addition of equipment;
74 - second addition amount basic calculation unit; 75 - a control target value extracting unit;
621a, 62lb - a rising correction value specification part; 622a, 622b - a concentration amount calculating unit;
623a, 623b - base additive amount calculating unit; 624a, 624b -Definition of downward correction value;
625a, 625b - Regulation for Additive Amount; 626a, 626b - Addition amount calculating section
Claims (13)
A first acidic gas concentration measuring step (first acidic gas concentration measuring step) for measuring the concentration of the first acidic gas in the treated exhaust gas after the treatment of the discharged exhaust gas in a dust collector,
Calculating first acid gas information that is information on the first acid gas based on the first acid gas concentration, calculating a normal addition amount of the first alkali agent based on the first acid gas information, A first calculating step (first producing step) of calculating first adding amount information on the basis of the first adding amount information,
A second acidic gas concentration measuring step (second acidic gas concentration measuring step) for measuring the concentration of the second acidic gas in the second acidic gas, which is an untreated flue gas discharged from the dust collector,
Calculating second acid gas information that is information on the second acid gas based on the second acid gas concentration, calculating an addition amount of the second alkaline agent based on the second acid gas information, A second calculating step (second producing step) of calculating second adding amount information,
A first adding step (first adding step) of adding the first alkaline agent of the first addition amount to the combustion exhaust gas,
And a second adding step (second adding step) of adding the second alkaline agent of the second added amount to the combusted exhaust gas
≪ / RTI >
Wherein the first additive amount information includes a control target value which is a target value of the first acidic gas concentration in the post-
Wherein the second calculation step calculates the second addition amount based on a concentration obtained by subtracting (subtracting) the control target value from the second acid gas concentration.
The second acidic gas information may include an acidic gas concentration (a concentration of acidic gas) indicating a rate of change of an instantaneous acidic gas concentration (instantaneous acidic gas concentration) which is a real time acidic gas concentration measured in the second acidic gas concentration measuring step / RTI >
The first calculation step calculates the normal addition amount of the first alkali agent based on the first acid gas information and corrects the normal addition amount based on the predetermined correction method according to the acid gas concentration amount , And then the first addition amount information is calculated based on the normal addition amount .
The basic addition amount correspondence information associating the instant acid gas concentration and the addition amount of the first alkaline agent in advance is defined,
The first calculation step calculates the normal addition amount on the basis of the instantaneous acid gas concentration and the basic addition amount corresponding to reduction information when the acid gas concentration amount is in a descending state in which the amount of acid gas is kept constant or decreasing ,
In addition, for the acid when the rising state in which the gas concentration increases the amount of the moment based on the acid gas concentration and also the basic addition amount by increasing the value of the acid gas concentration in the correspondence information smaller by a predetermined correction method of And the normal addition amount is calculated on the basis of the basic addition amount correspondence information.
Wherein the first calculating step is a step of calculating the normal addition amount by a fall correction value that is in a range of more than 0 and less than 1, which is predefined, when the acid gas concentration amount is in a falling state, Wherein the acid gas stabilization treatment method comprises:
Wherein the first calculating step is a step of calculating the normal addition amount by a fall correction value that is in a range of more than 0 and less than 1, which is predefined, when the acid gas concentration amount is in a falling state, Wherein the acid gas stabilization treatment method comprises:
A plurality of corresponding additive upper limit values are set between a maximum addition amount and a minimum addition amount which can be added in the first addition step,
Wherein the plurality of upper limits of the corresponding additive amounts respectively correspond to a plurality of acidic gas concentrations,
Wherein the second acidic gas information includes an instantaneous acidic gas concentration which is an acidic gas concentration measured in the second acidic gas concentration measuring step,
Wherein the first calculation step is a step of calculating the concentration of the acid gas having the concentration corresponding to the higher concentration among the two adjacent acid gas concentrations when the instantaneous acid gas concentration is within the range of two adjacent acid gas concentrations out of the plurality of acid gas concentrations And the normal addition amount is calculated on the basis of the upper limit value.
Wherein the first acid gas information includes an average acid gas concentration which is an average value of the first acid gas concentration at a predetermined time,
Wherein the first calculation step calculates the first addition amount information based on a predetermined emergency addition amount instead of the normal addition amount when the average acid gas concentration exceeds the predetermined emergency addition concentration. Gas stabilization treatment method.
The second acidic gas may include a hydrogen chloride gas (hydrogenated gas) and / or a sulfur oxide gas (sulfur oxide gas)
The second acidic gas concentration measuring step may include a hydrogen chloride gas concentration measuring step of measuring the concentration of the hydrogen chloride gas in the second acidic gas when the second acidic gas contains hydrogen chloride gas, And a sulfur oxide concentration measuring step of measuring a sulfur oxide concentration in the second acidic gas when the sulfuric acid gas contains sulfur oxide gas, and when the second acidic gas contains both the hydrogen chloride gas and the sulfur oxide gas The hydrogen chloride gas concentration measuring step and the sulfur oxide concentration measuring step ,
Wherein the second acidic gas information includes hydrogen chloride information on the hydrogen chloride gas and / or sulfur oxide information on the sulfur oxide gas,
Wherein the first calculation step calculates the normal addition amount based on the hydrogen chloride gas addition amount calculated on the basis of the hydrogen chloride information and / or the sulfur oxide gas addition amount and / or the basic addition amount calculated on the basis of the sulfur oxide information,
Wherein the base addition amount is calculated based on an average addition amount of the first addition amount information at a predetermined time.
Wherein the first alkaline agent is an alkaline agent containing a fine powder of fine powder of at least 5 to 30 mu m,
Wherein the second alkaline agent is an alkaline agent containing at least slaked lime.
The addition amount of the first alkaline agent is 0.1 to 0.6 equivalents per acidic gas concentration before adding the alkali agent,
Wherein the amount of the second alkaline agent added is 0.5 to 3.0 equivalents per acidic gas concentration before addition of the alkaline agent.
(Immobilization process) in which at least one selected from iron-based compounds (iron compounds), phosphoric acid-containing compounds (phosphoric acid-containing compounds) and neutralizers is added to fly ash collected in the dust collector Further comprising the step of treating the acid gas.
A dust collector,
An inflow path (inflow path) for introducing the combustion exhaust gas into the dust collector,
A discharge path (discharge path) for discharging the processed discharge gas from the dust collector after being treated in the dust collector,
A first acidic gas measurement device (first acidic gas measurement device) for performing the first acidic gas concentration measurement step and outputting the first acidic gas concentration measurement signal as a first acidic gas information signal,
A second acidic gas measurement device (second acidic gas measurement device) for performing the second acidic gas concentration measurement step and outputting the second acidic gas concentration measurement signal as a second acidic gas information signal,
A first addition amount calculation unit for executing the first calculation step on the basis of the first acid gas information signal to output the first addition amount as a first addition amount signal and a second addition amount calculation unit for calculating the second calculation amount And a second addition amount calculating section for executing the second addition amount signal and outputting the second addition amount as a second addition amount signal,
A first addition device (first addition device) for executing the first addition process on the basis of the first addition amount signal,
A second addition device (second addition device) for executing the second addition process based on the second addition amount signal
The combustion and exhaust gas treatment facility equipped.
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| KR102282158B1 (en) * | 2021-01-26 | 2021-07-27 | 현대제철 주식회사 | Composition for inhibiting the elution of heavy metals from desulfurization waste and method for inhibiting the elution of heavy metals from desulfurization waste using the same |
| CN113483339B (en) * | 2021-06-16 | 2023-08-25 | 江苏凯丰新能源科技有限公司 | Continuous electric heating furnace and method for recycling aluminum electrolysis carbon electrode waste |
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