JP4831833B2 - CO2 recovery device and waste treatment method in CO2 recovery device - Google Patents

Description

The present invention relates to a CO ₂ recovery device that processes waste generated when removing CO _{2 and the} like in exhaust gas, and a waste processing method in the CO ₂ recovery device .

In recent years, the greenhouse effect due to CO ₂ has been pointed out as one of the causes of global warming, and countermeasures have become urgent internationally to protect the global environment. The source of CO ₂ extends to all human activity fields that burn fossil fuels, and there is a tendency for the demand for emission control to become stronger. Along with this, for a power generation facility such as a thermal power plant that uses a large amount of fossil fuel, a method for removing the CO ₂ in the combustion exhaust gas by bringing the combustion exhaust gas of the boiler into contact with the amine-based CO ₂ absorbent and recovering it, and A method of storing the recovered CO ₂ without releasing it to the atmosphere has been energetically studied.

Moreover, as a process of removing and recovering CO ₂ from the combustion exhaust gas using the CO ₂ absorption liquid as described above, a process of bringing the combustion exhaust gas and the CO ₂ absorption liquid into contact in an absorption tower, an absorption liquid that has absorbed CO ₂ Is used in the regeneration tower to liberate CO ₂ and regenerate the absorption liquid, which is then recycled to the absorption tower and reused (see, for example, Patent Document 1).

As shown in FIG. 4, a conventional CO ₂ recovery apparatus 1000A is configured to cool an exhaust gas 1002 containing CO ₂ discharged from industrial equipment 1001 such as a boiler with cooling water 1003 in a cooling tower 1004, and in the absorption tower 1006 flue gas 1002 containing _2, CO ₂ -absorbing solution 1005 and countercurrent contact based on alkanolamine, CO ₂ in the flue gas 1002 is absorbed by the CO ₂ absorbing solution 1005, CO from the flue gas 1002 Remove ₂ Then, CO ₂ absorbent having absorbed CO ₂ (rich solution) 1007 releases CO ₂ in the regeneration tower 1008, the time to reach the lower regenerator 1008, CO ₂ most are removed, the lean solution 1009 As described above, the CO ₂ absorbent 1005 is regenerated. This regenerated CO ₂ absorbent 1005 is sent again to the absorption tower 1006 and reused.

Further, in the conventional CO ₂ recovery apparatus 1000A, SOx remaining without being removed in the desulfurization process reacts with the alkanolamine contained in the CO ₂ absorbent 1005 in the deCO ₂ process to form a heat-stable salt. Not only is it generated, but when CO ₂ in the exhaust gas is recovered, the amine is deteriorated by oxygen to produce a heat-stable salt, which is contained in the lean solution 1009. Since this heat stable salt is not removed under normal conditions in the process of regenerating the lean solution 1009 from the rich solution 1007, it gradually accumulates in the system as the lean solution 1009 circulates. Therefore, the conventional CO ₂ recovery apparatus 1000A includes a reclaimer 1040 that heat-concentrates and removes deterioration products such as salts remaining in the lean solution 1009 generated in the regeneration tower 1008. The lean solution 1009 generated in the regeneration tower 1008 is extracted on the lean solution supply line 1022 to the extraction line 1041, and the reclaimer 1040 is configured to remove deteriorated substances such as salts remaining in the lean solution 1009. The lean solution 1009 was heated to, for example, 130 to 150 ° C., and the CO ₂ absorbent evaporated from the lean solution 1009 was fed to the bottom of the regeneration tower 1008. The waste concentrated at the bottom of the reclaimer 1040 is a mixed waste in which an inorganic substance is contained in addition to an organic substance, and the organic substance and the inorganic substance are mixed. The mixed waste 1051 is supplied to the waste combustion apparatus 1053 via the waste discharge line 1052 and discharged, for example, using a pump or the like.

In the conventional CO ₂ recovery apparatus 1000B, as shown in FIG. 5, an ion exchange tower 1023 is provided between the absorption tower 1006 and the regeneration tower 1008, and a part of the lean solution 1009 is extracted. After ion exchange in the ion exchange tower 1023, the ion solution is returned to the lean solution supply line 1022 (see, for example, Patent Document 2).

Japanese Patent No. 3716195 US Pat. No. 4,624,839

However, in the conventional CO ₂ recovery apparatus 1000A, since the mixed waste 1051 discharged from the reclaimer 1040 contains an inorganic substance together with an organic substance, it is incinerated using a special apparatus as the waste combustion apparatus 1053. There is a problem that the cost is increased.

Further, in the conventional CO ₂ recovery apparatus 1000B, the ion exchange tower 1023 and the reclaimer 1040 are installed in separate lines, so that only by extracting a part of the lean solution 1009 into the ion exchange tower 1023. Only a part of the extracted lean solution 1009 can be ion-exchanged, and the inorganic acid in the whole circulating lean solution 1009 cannot be sufficiently removed.

  Therefore, the inorganic solution remains in the lean solution 1009 extracted into the reclaimer 1040, and separation of the inorganic substance and the organic substance becomes insufficient, and the organic waste and the inorganic waste in the mixed waste are removed by the reclaimer 1040. There is a problem that they must be processed together.

  Further, when the entire amount of the circulating lean solution 1009 is extracted and processed in the ion exchange process, the inorganic acid in the lean solution 1009 can be removed to a high degree, but the ion exchange column 1023 needs to be enlarged. There is a problem that there is.

Further, in the future, when the CO ₂ recovery device becomes larger and the amount of CO ₂ to be processed becomes, for example, 1000 t or more per day, it is necessary to increase the capacity of the reclaimer 1040. Therefore, the conventional CO ₂ recovery device becomes larger. There is a problem that the cost increases.

In view of the above problems, the present invention provides CO _{2 and the} like in exhaust gas. To provide a CO ₂ recovery device capable of efficiently treating organic waste and inorganic waste in waste generated when removing CO2 and a waste treatment method in the CO ₂ recovery device Is an issue.

The first aspect of the present invention to solve the above problems, an absorption tower for removing CO ₂ by contacting the gas with CO ₂ absorbing liquid containing CO _2, the rich solution that has absorbed CO ₂ A regeneration tower for regenerating and exchanging heat, and a CO ₂ recovery device for reusing the lean solution from which CO ₂ has been removed in the regeneration tower in the absorption tower, wherein a part of the lean solution produced in the regeneration tower is Lean solution extraction line to be extracted, an anion exchange part for removing inorganic acid and organic acid in the lean solution extracted in the lean solution extraction line by ion exchange, and a downstream side of the anion exchange part A first reclaimer for heating the lean solution from which the inorganic acid and the organic acid have been removed in the anion exchange unit and evaporating the CO ₂ absorbing solution remaining in the lean solution ; First rickle In a vaporized the CO ₂ absorbing solution the regeneration tower in the bottom vaporizer CO ₂ absorbing solution feed to be supplied to the side line of the first lean solution inorganic and organic acids are removed by reclaimer An organic waste discharge line for extracting a neutral organic compound and a basic organic compound as organic waste from the first reclaimer; and an alkaline solution supply unit for supplying an alkaline agent to the anion exchange unit; Inorganic main waste discharge for separating the anionic exchange resin from the anion exchange resin with the alkali agent and using the inorganic acid and organic acid eluted in the solution as the inorganic main waste and discharging the solution containing the inorganic main waste And a CO ₂ recovery device characterized by comprising a line .

A second invention is a solid-liquid separation according to the first invention, which is provided on the upstream side of the anion exchange part and solid-liquid separates the solid matter remaining in the lean solution extracted in the lean solution extraction line. A CO ₂ recovery apparatus having a separation unit.

3rd invention has 1st recycling line which returns the said lean solution from which the solid substance was removed in the said solid-liquid separation part to the upstream of the said solid-liquid separation part in 1st or 2nd invention. It is in the CO ₂ recovery device characterized by this.

According to a fourth invention, in any one of the first to third inventions, the lean solution from which the inorganic acid and the organic acid have been removed in the anion exchange part is obtained by combining the solid-liquid separation part and the anion exchange part. A CO ₂ recovery apparatus having a second recycle line that returns in between.

According to a fifth invention, in the invention of the first or 2, to a solution containing the separated said inorganic metallic waste by the alkali agent is supplied to the anion-exchange unit from the alkaline solution supplying unit, supplying a sulfuric acid in the CO ₂ recovery apparatus characterized by comprising a sulfuric acid supply unit for.

A sixth invention is the CO ₂ recovery apparatus according to the fifth invention, further comprising a water supply unit for supplying water to the solution containing the inorganic main waste supplied with the sulfuric acid. .

A seventh invention includes the inorganic main waste to which the sulfuric acid is supplied provided in the inorganic main waste discharge line between the sulfuric acid supply unit and the water supply unit in the sixth invention. A CO ₂ recovery apparatus having a second reclaimer for removing organic waste remaining in the solution.

According to an eighth aspect of the present invention, in the fifth aspect , the organic waste remaining in the solution including the inorganic main waste to which the sulfuric acid is supplied is provided on the downstream side of the sulfuric acid supply unit. The CO ₂ recovery apparatus includes an oxidation treatment tank that performs an oxidation treatment with an organic oxidant supplied from a supply unit.

According to a ninth invention, in any one of the first to eighth inventions, the position where the part of the lean solution in the lean solution extraction line is extracted is immediately before the absorption tower, the rich solution and the lean solution. Between the heat exchanger that exchanges heat with each other and a cooler provided between the heat exchanger and the absorption tower, or between the heat exchanger and the regeneration tower. In the CO ₂ recovery unit.

A tenth aspect of the present invention is the lean solution according to any one of the first to ninth aspects, wherein the solid matter is removed in the solid-liquid part separation part between the solid-liquid separation part and the anion exchange part. A CO ₂ recovery device having a turbidimeter for measuring the degree of turbidity therein.

An eleventh invention, the gas and the CO ₂ absorbing liquid containing CO ₂ into contact in the absorption tower to remove CO _2, and regeneration in regenerator rich solution that has absorbed CO ₂ by heat exchange, the regeneration A waste treatment method in a CO ₂ recovery device that reuses a lean solution from which CO ₂ has been removed by a tower, wherein the lean solution is partly extracted to a lean solution extraction line, and the lean solution is anion. In the anion exchange resin that is fed to the exchange unit and filled in the anion exchange unit , the inorganic acid and organic acid in the extracted lean solution are ion-exchanged to remove the inorganic acid and organic acid. The prepared lean solution is fed to the first reclaimer, and the lean solution from which the inorganic acid and the organic acid have been removed is heated in the anion exchange unit using the first reclaimer , and remains in the lean solution. Do It evaporated serial CO ₂ absorbing solution, the CO ₂ absorbent that has vaporized in the first reclaimer is supplied to the bottom side of the regeneration tower through a vaporized CO ₂ absorbing solution supply line, the CO ₂ absorbing solution Is recovered in the regeneration tower, and the neutral organic compound and the basic organic compound in the lean solution from which the inorganic acid and the organic acid have been removed by the first reclaimer are used as the organic waste as the first reclaimer. withdrawn through an organic waste discharge line to remove the organic waste from, when reproducing the anion-exchange resin filled in the anion exchange section, the anion-exchange unit into alkaline agent The inorganic acid and the organic acid that are ion-exchanged by adhering to the anion exchange resin are separated from the anion exchange resin, and the inorganic acid and the organic acid eluted into the solution as a salt of the inorganic acid and the organic acid. Organic acids mainly inorganic A waste treatment method in a CO ₂ recovery apparatus , characterized in that a waste solution is prepared by adding sulfuric acid to a solution containing the inorganic main waste, adjusting the pH, diluting with water, and discharging the solution below a reference value. is there.

In a twelfth aspect based on the eleventh aspect , before the inorganic acid and the organic acid in the lean solution from which a part of the lean solution has been extracted is removed by ion exchange, the solid that remains in the lean solution in advance is removed. The present invention resides in a waste treatment method in a CO ₂ recovery device characterized by separating and removing a solid-liquid product.

A thirteenth invention, in the invention of the eleventh or 12, by adding an alkali agent to the anion exchange part, the solution containing the inorganic metallic wastes, the pH was prepared by adding sulfuric acid, the second The present invention provides a waste treatment method in a CO ₂ recovery device, wherein organic waste remaining in a solution containing the inorganic main waste is further removed using a reclaimer.

A fourteenth invention is the invention of the first 12 or 13, by adding an alkali agent to the anion exchange part, the solution containing the inorganic metallic wastes, the pH was prepared by adding sulfuric acid, oxidation treatment tank after pooled predetermined amount, the addition of organic oxidizing agent in the oxidation treatment tank, the organic waste remaining in the solution containing the inorganic metallic waste oxidation treatment, further characterized in that the removal It is in a waste treatment method in a CO ₂ recovery device .

According to the present invention, since the anion exchange part and the reclaimer are arranged in series, the inorganic acid and the organic acid in the partially extracted lean solution are removed by ion exchange, and the organic system is removed with a reclaimer. By treating the waste, the organic waste and the inorganic main waste in the mixed waste can be separated and processed efficiently with a compact facility.
In addition, since the incineration process in the waste incinerator can target only the organic waste, the amount of waste can be reduced.

  Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

A CO ₂ recovery device according to a first embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view of a CO ₂ recovery apparatus according to Embodiment 1 of the present invention. In the figure, the same components as those of the CO ₂ recovery apparatus shown in FIG. Omitted.
Also, in the figure, the industrial equipment 1001 and the cooling tower 1004 shown in FIG. 4 are omitted, and a circulation system of the absorption tower 1006, the regeneration tower 1008, and the lean solution 1009 therebetween is shown.

As shown in FIG. 1, CO ₂ recovery apparatus 10A according to the present embodiment, absorption by contacting the gas and the CO ₂ absorbing solution 1005 containing CO ₂ and absorption tower 1006 for removing CO _2, the CO ₂ A regeneration tower 1008 for regenerating and exchanging heat with the rich solution 1007, and a CO ₂ recovery device for reusing the lean solution 1009 from which CO ₂ has been removed in the regeneration tower 1008 in the absorption tower 1006, A lean solution extraction line 11 for extracting a part of the generated lean solution 1009, and a solid-liquid separation unit for solid-liquid separation of solids remaining in the lean solution 1009A extracted in the lean solution extraction line 11 12 and anion exchange that removes the inorganic acid and the organic acid in the lean solution 1009B from which solids have been removed in the solid-liquid separation unit 12 by ion exchange 13, together with inorganic and organic acids to remove the organic waste in the lean solution 1009C removed, and a first reclaimer 1040-1 for recovering CO ₂ absorbing solution in the regeneration tower 1008 It will be.
Here, in this invention, an organic acid means the organic compound which shows acidity.

In the CO ₂ recovery apparatus 10A according to the present embodiment, the lean solution extraction line 11 is provided immediately before the absorption tower 1006, and a part of the lean solution 1009 is extracted. The lean solution 1009A containing solids in the lean solution 1009A extracted from the lean solution extraction line 11 is defined as the lean solution 1009A.

  The lean solution 1009 </ b> A extracted from the lean solution extraction line 11 is supplied to the solid-liquid separation unit 12 through the lean solution extraction line 11.

  In the solid-liquid separation unit 12, the solid matter remaining in the lean solution 1009A can be subjected to solid-liquid separation, and the solid matter can be removed from the lean solution 1009A. Further, the lean solution 1009A from which the solid matter is removed from the lean solution 1009A is referred to as a lean solution 1009B. Moreover, as said solid substance, there exists a dust etc. which are discharged | emitted from waste gas etc., for example.

Further, in the CO ₂ recovery apparatus 10A according to the present embodiment, the lean solution 1009B from which the solid matter has been removed from the lean solution 1009A in the solid-liquid separation unit 12 is disposed on the downstream side of the solid-liquid separation unit 12. A first recycle line 14 that returns to the upstream side of the solid-liquid separator 12 is provided.

  The solid solution remaining in the lean solution 1009B is again removed by the solid-liquid separation unit 12 by returning the lean solution 1009B to the upstream side of the solid-liquid separation unit 12 by the first recycling line 14. Therefore, the solid matter remaining in the lean solution 1009B can be more reliably removed.

  In addition, the number of times the lean solution 1009B is extracted by the first recycle line 14 is not particularly limited, and the lean solution 1009B can be repeated any number of times until the solid matter remaining in the lean solution 1009B is reliably removed. You may make it extract.

Further, in the CO ₂ recovery apparatus 10A according to the present embodiment, in the lean solution 1009B in which the solid matter is removed in the solid-liquid separation unit 12 between the solid-liquid separation unit 12 and the anion exchange unit 13. A turbidimeter 15 for measuring the degree of turbidity is provided.

  By measuring the degree of turbidity in the lean solution 1009B with the turbidimeter 15, the solid-liquid separation unit 12 can confirm the degree of removal of the solid matter. Depending on the measurement result of the turbidimeter 15, the solid solution is removed from the lean solution 1009 B again by the solid-liquid separation unit 12 through the first recycle line 14 or is supplied to the anion exchange unit 13. You can decide what to do.

Further, the CO ₂ recovery apparatus 10A according to the present embodiment includes the anion exchange unit 13 that performs ion exchange with the inorganic acid and the organic acid in the lean solution 1009B. Here, the anion exchange part 13 is filled with an anion exchange resin.

  Since the inorganic acid and the organic acid in the lean solution 1009B are acidic, they adhere to the anion exchange resin filled in the anion exchange part 13 and are ion exchanged. Thereby, an inorganic acid and an organic acid can be removed from the lean solution 1009B. The lean solution 1009B from which the inorganic acid and the organic acid have been removed from the lean solution 1009B is referred to as a lean solution 1009C.

Further, in the CO ₂ recovery apparatus 10A according to this embodiment, the lean solution 1009C from which the inorganic acid and the organic acid have been removed in the anion exchange unit 13 is disposed downstream of the anion exchange unit 13 in the solid-liquid separation unit. 12 and a second recycle line 16 that returns between the anion exchanger 13.

  By returning the lean solution 1009C between the solid-liquid separation unit 12 and the anion exchange unit 13 by the second recycle line 16, the anion exchange unit 13 again remains in the lean solution 1009C. Since the inorganic acid and organic acid to be removed can be removed, the inorganic acid and organic acid remaining in the lean solution 1009C can be reliably removed.

  In addition, the number of times that the lean solution 1009C is extracted by the second recycle line 16 is not particularly limited, and any number of times until the inorganic acid and the organic acid remaining in the lean solution 1009C are reliably removed. The lean solution 1009C may be extracted.

  Examples of the organic acid in the present invention include formic acid, acetic acid, propionic acid, 2-methylpropionic acid, oxalic acid, tartaric acid, butyric acid, valeric acid, succinic acid, citric acid, maleic acid, glutamic acid, benzenesulfonic acid, etc. And sulfinic acids such as benzenesulfinic acid and paratoluenesulfinic acid.

  Examples of inorganic acids include hydrogen halides such as hydrochloric acid, odorous acid, iodic acid, and hydrofluoric acid, and phosphoric acids such as sulfuric acid, sulfurous acid, nitric acid, nitrous acid, boric acid, silicic acid, phosphoric acid, polyphosphoric acid, and phosphorous acid. Is mentioned.

Further, in the CO ₂ recovery apparatus 10A according to the present embodiment, an alkaline solution supply unit 18 that supplies an alkaline agent such as a sodium hydroxide aqueous solution 17 to the anion exchange unit 13, and an inorganic acid and an organic acid eluted. And an inorganic main waste discharge line 20 for discharging the solution 19 containing the main waste.

  When the anion exchange resin filled in the anion exchange unit 13 is regenerated, an aqueous solution of sodium hydroxide 17 is supplied to the anion exchange unit 13 to exchange inorganic and organic acids. It can be separated from the resin and eluted in solution. As a result, the anion exchange resin is regenerated, and the inorganic acid waste discharged from the anion exchange unit 13 and the solution 19 containing the inorganic main waste from which the organic acid is eluted are passed through the inorganic main waste discharge line 20. It is possible to treat only the inorganic main waste containing the inorganic acid and the organic acid.

Further, in the CO ₂ recovery apparatus 10A according to the present embodiment, the solution containing the inorganic main waste separated by the sodium hydroxide aqueous solution 17 supplied from the alkaline solution supply unit 18 to the anion exchange unit 13. A sulfuric acid supply unit 22 that supplies sulfuric acid (H ₂ SO ₄ ) 21 to 19 is provided.

  Since the solution 19 containing the inorganic main waste is the sodium hydroxide aqueous solution 17 and is basic, the sulfuric acid 21 is supplied from the sulfuric acid supply unit 22 to the solution 19 containing the inorganic main waste. Thus, the pH of the solution 19 containing the inorganic main waste can be adjusted. As a result, the pH of the solution 19 containing the inorganic main waste can be set to 7.0, for example, to be a neutral solution.

In the CO ₂ recovery apparatus 10A according to this embodiment, the water supply unit 24 supplies the water 23 to the solution 19 containing the inorganic main waste after the sulfuric acid 21 is supplied from the sulfuric acid supply unit 22. To have.

  By supplying the water 23 from the water supply unit 24 to the solution 19 containing the inorganic main waste, the solution 19 containing the inorganic main waste adjusted for pH is diluted, and the inorganic main waste is removed. Since the COD value in the solution 19 that contains it can be lowered, the COD value of the solution 19 that contains the inorganic main waste can be discharged as a reference value or less.

Further, in the CO ₂ recovery apparatus 10A according to the present embodiment, the organic waste in the lean solution 1009C from which the inorganic main waste ion-exchanged by the anion exchange unit 13 has been removed is removed, and the CO _{2 is} recovered. _{(2) A} first reclaimer 1040-1 for collecting the absorbing liquid in the regeneration tower 1008 is provided.

  Further, among the organic wastes in the lean solution 1009C, acidic organic compounds are removed in the anion exchange unit 13, so in this embodiment, what is the organic waste remaining in the lean solution 1009C? A neutral organic compound or a basic organic compound.

  The lean solution 1009C from which the inorganic acid and the organic acid sent to the first reclaimer 1040-1 are removed is saturated by the saturated steam 1046 supplied from the saturated steam supply line 1045 in the first reclaimer 1040-1. The lean solution 1009C from which the inorganic main waste has been removed is heated through the steam supply pipe 1050 in the reclaimer 1040.

Further, the CO ₂ absorbing solution in the lean solution 1009C has a lower boiling point than the organic waste 25 that is a neutral organic compound or a basic organic compound, and vaporizes at 135 ° C., for example.

Organic compounds of the CO ₂ absorbing solution and neutral, the boiling point difference between the basic organic compound, the first reclaimer 1040-1 CO ₂ absorbing solution is vaporized in 1047, vaporized CO ₂ absorbing solution with steam It is fed to the bottom of the regeneration tower 1008 via a supply line 1048.

  In addition, by heating the lean solution 1009, the organic waste 25 in the lean solution 1009 is concentrated on the inner bottom of the first reclaimer 1040-1. The heat-concentrated organic waste 25 is extracted from the first reclaimer 1040-1 and sent to the waste incinerator 27 through the organic waste discharge line 26.

The incineration process in the waste incinerator 27 can target only the organic waste 25. For this reason, the waste incinerator 27 reduces the amount of waste treated by, for example, about 40%, compared with the waste combustion apparatus 1053 of the conventional CO ₂ recovery apparatuses 1000A and 1000B as shown in FIGS. Can be achieved.

Further, in the CO ₂ recovery apparatus 10A according to the present embodiment, the position at which a part of the lean solution 1009 is extracted from the lean solution extraction line 11 is set immediately before the absorption tower 1006 on the downstream side of the cooler 1021. However, the present invention is not limited to this. The position at which a part of the lean solution 1009 of the lean solution extraction line 11 is extracted is, for example, between the heat exchanger 1013 and the cooler 1021 or on the upstream side of the heat exchanger 1013. 1007 and the lean solution 1009 may be in any of the positions before and after the heat exchanger 1013 for exchanging heat with each other.

In the CO ₂ recovery apparatus 10A according to the present embodiment, the temperature of the lean solution 1009 immediately before the absorption tower 1006 on the downstream side of the cooler 1021 is, for example, about 40 ° C., and the heat exchanger 1013 The temperature of the lean solution 1009 between the cooler 1021 and the cooler 1021 is, for example, about 60 ° C., and the temperature of the lean solution 1009 upstream of the heat exchanger 1013 is about 120 ° C.

  Here, a solid-liquid separation filter (not shown) used for the solid-liquid separation unit 12 and the anion exchange resin in the anion exchange unit 13 are supplied to the solid-liquid separation unit 12 in order to avoid deterioration. The solution is preferably cold.

  Therefore, when the lean solution 1009 between the heat exchanger 1013 and the cooler 1021 or the lean solution 1009 on the upstream side of the heat exchanger 1013 is used, the solid-liquid is supplied to the lean solution extraction line 11. It is necessary to separately provide a cooler on the upstream side of the separation unit 12, cool the temperature of the extracted lean solution 1009 A to, for example, 40 ° C. to 50 ° C. or less, and then send it to the solid-liquid separation unit 12 It is.

  Therefore, it is preferable that the position where the lean solution 1009 is extracted be the position immediately before the absorption tower 1006 in the downstream of the cooler 1021 where the temperature of the lean solution 1009 is low.

As described above, according to the CO ₂ recovery apparatus 10A according to the present embodiment, the anion exchange is performed by using only a part of the CO ₂ absorbent extracted from the lean solution extraction line 11 and only the lean solution 1009A. By disposing the part 13 and the first reclaimer 1040-1 in series, after removing the organic acid and the inorganic acid by ion exchange, the organic waste remaining in the lean solution 1009A after ion exchange Object 25 can be processed. In addition, since the organic main waste of the organic acid and inorganic acid removed by ion exchange can be treated, the organic waste 25 and the inorganic waste can be efficiently used with a compact facility. Can be separated and processed separately.

  In addition, since the incineration process in the waste incinerator 27 can target only organic waste, the amount of waste processed can be reduced.

As a result, for example, even in the case of a CO ₂ recovery device having a CO ₂ recovery amount of, for example, 1000 t or more per day, the organic waste and the inorganic waste in the mixed waste are separately separated without increasing the size of the device. It can be processed efficiently.

A CO ₂ recovery device according to a _second embodiment of the present invention will be described with reference to FIG.
FIG. 2 is a schematic diagram illustrating the configuration of the CO ₂ recovery apparatus according to the present embodiment.
Since the CO ₂ recovery apparatus according to the present embodiment is the same as the configuration of the CO ₂ recovery apparatus according to the first embodiment, the same reference numerals are given to the same members, and duplicate descriptions are omitted.
As in FIG. 1, the industrial equipment 1001 and the cooling tower 1004 shown in FIG. 4 are omitted in the figure, and a circulation system of the absorption tower 1006, the regeneration tower 1008, and the lean solution 1009 therebetween is shown.
As shown in FIG. 2, the CO ₂ recovery apparatus 10B according to the present embodiment is provided in the inorganic main waste discharge line 20 of the CO ₂ recovery apparatus 10A shown in FIG. 1, and after the sulfuric acid 21 is supplied. It further includes a second reclaimer 1040-2 for removing the organic waste 25 remaining in the solution 19 containing the inorganic main waste.

In the CO ₂ recovery apparatus 10B according to the present embodiment, the sulfuric acid 21 is supplied to the solution 19 containing the inorganic main waste discharged through the first inorganic main waste discharge line 20-1, and the pH is adjusted. Adjustments are made, for example, neutrality. Then, the solution 19 containing the inorganic main waste whose pH is adjusted with the sulfuric acid 21 is supplied to the second reclaimer 1040-2.

  In the second reclaimer 1040-2, the solution 19 containing the inorganic main waste is passed through the steam supply pipe 1050 in the second reclaimer 1040-2 by the saturated steam 1046 supplied from the saturated steam supply line 1045. Then, the solution 19 containing the inorganic main waste is heated.

As a result, the organic waste 25 remaining in the solution 19 containing the inorganic main waste is evaporated and sent to the waste incinerator 27 via the second organic waste discharge line 26-2. ,
The organic waste 25 remaining in the solution 19 containing the inorganic main waste can be removed.

  Then, the organic waste 25 fed to the waste incinerator 27 via the second organic waste discharge line 26-2 is processed in the waste incinerator 27.

The incineration process in the waste incinerator 27 can target only the organic waste 25 recovered from the first reclaimer 1040-1 and the second reclaimer 1040-2. For this reason, the waste incinerator 27 reduces the amount of waste to be treated by, for example, about 35%, compared with the waste combustion apparatus 1053 of the conventional CO ₂ recovery apparatuses 1000A and 1000B as shown in FIGS. Can be achieved.

  Further, the solution containing the inorganic main waste from which the organic waste 25 left by distillation of the solution 19 containing the inorganic main waste in the second reclaimer 1040-2 is distilled. 19 is discharged from the second reclaimer 1040-2 via the second inorganic main waste discharge line 20-2.

Further, the CO ₂ recovery apparatus 10B according to the present embodiment includes a water supply unit 24 that supplies the water 23 to the solution 19 containing the inorganic main waste discharged from the second reclaimer 1040-2. I have to.

  By diluting the solution 19 containing the inorganic main waste discharged from the second reclaimer 1040-2 by supplying the water 23 to the solution 19 containing the inorganic main waste from the water supply unit 24. In addition, since the COD value in the solution 19 containing the inorganic main waste can be lowered, the COD value of the solution 19 containing the inorganic main waste can be discharged with a reference value or less.

Further, the amount of the water 23 supplied from the water supply unit 24 is removed from the organic waste 25 remaining in the solution 19 containing the inorganic main waste in the second reclaimer 1040-2. Therefore, the amount of water necessary for diluting the inorganic main waste is sufficient. For this reason, the amount of water 23 supplied from the water supply unit 24 is larger than the amount of water 23 supplied from the water supply unit 24 in the CO ₂ recovery apparatus 10A according to the first embodiment. For example, the amount of water 23 can be reduced by about 35%.

Thus, according to the CO ₂ recovery apparatus 10B according to the present embodiment, the second reclaimer disposed in the inorganic main waste discharge line 20 between the sulfuric acid supply unit 22 and the water supply unit 24. In 1040-2, the organic waste 25 remaining in the solution 19 containing the inorganic main waste can be removed. Thereby, even when the organic waste 25 remains in the solution 19 containing the inorganic main waste, the remaining organic waste 25 is removed from the solution 19 containing the inorganic main waste. Can do.

Further, since the amount of water 23 supplied from the water supply unit 24 is sufficient for diluting the inorganic main waste, the water is more than the CO ₂ recovery apparatus 10A according to the first embodiment. The amount of water 23 supplied from the supply unit 24 can be reduced.

A CO ₂ recovery device according to a third embodiment of the present invention will be described with reference to FIG.
FIG. 3 is a schematic diagram illustrating the configuration of the CO ₂ recovery apparatus according to the present embodiment.
Since the CO ₂ recovery apparatus according to the present embodiment is the same as the configuration of the CO ₂ recovery apparatus according to the first embodiment, the same reference numerals are given to the same members, and duplicate descriptions are omitted.
As in FIG. 1, the industrial equipment 1001 and the cooling tower 1004 shown in FIG. 4 are omitted in the figure, and a circulation system of the absorption tower 1006, the regeneration tower 1008, and the lean solution 1009 therebetween is shown.
As shown in FIG. 3, the CO ₂ recovery apparatus 10C according to the present embodiment is provided on the downstream side of the sulfuric acid supply unit 22, and in the solution 19 containing the inorganic main waste after the sulfuric acid 21 is supplied. It further includes an oxidation treatment tank 32 that performs an oxidation treatment of the remaining organic waste 25 with an organic oxidant 31 supplied from an organic oxidant supply unit 30.
In this embodiment, since the inorganic main waste and the organic oxidant 31 can be collectively processed, the water supply unit 24 of the CO ₂ recovery apparatus 10A shown in FIG. 1 is omitted.

  Here, in this embodiment, the organic oxidant refers to an oxidant that decomposes an organic compound.

In the CO ₂ recovery apparatus 10C according to the present embodiment, the sulfuric acid 21 is supplied to the solution 19 containing the inorganic main waste, and the pH of the solution 19 containing the inorganic main waste is adjusted. It is trying to become. The solution 19 containing the inorganic main waste whose pH has been adjusted with the sulfuric acid 21 is fed to the oxidation treatment tank 32.

  The solution 19 containing the inorganic main waste is stored in the oxidation treatment tank 32 up to a predetermined amount. Then, after a predetermined amount of the solution 19 containing the inorganic main waste is stored in the oxidation treatment tank 32, the organic oxidant 31 is supplied from the organic oxidant supply unit 30 to the oxidation treatment tank 32. ing.

  Since the organic waste 25 remaining in the solution 19 containing the inorganic main waste is oxidized by the organic oxidant 31, the organic waste remaining in the solution 19 containing the inorganic main waste is oxidized. 25 can be decomposed.

Further, in the oxidation treatment tank 32, for example, the Fenton reaction of the following formula is performed by adding the organic oxidant 31. Divalent iron (Fe (II)) acts on hydrogen peroxide (H ₂ O ₂ ) to generate OH radicals (.OH), and the organic system is generated by the strong oxidizing power of these OH radicals (.OH). Waste 25 is decomposed.
Fe ²⁺ + H ₂ O ₂ → Fe ²⁺ + OH ⁻ + OH (1)

  Therefore, the organic waste 25 remaining in the solution 19 containing the inorganic main waste can be decomposed by adding the organic oxidant 31 to the solution 19 containing the inorganic main waste. it can.

The incineration process in the waste incinerator 27 can target only the organic waste 25 recovered from the first reclaimer 1040-1. For this reason, the waste incinerator 27 reduces the amount of waste treated by, for example, about 40%, compared with the waste combustion apparatus 1053 of the conventional CO ₂ recovery apparatuses 1000A and 1000B as shown in FIGS. Can be achieved.

  After the organic waste 25 remaining in the solution 19 containing the inorganic main waste is decomposed by the organic oxidant 31, the COD value of the solution 19 containing the inorganic main waste is set as a reference value. It can be released as:

Further, in the CO ₂ recovery apparatus 10C according to the present embodiment, the COD value of the solution 19 containing the inorganic main waste in the oxidation treatment tank 32 can be lowered to a predetermined reference value or less. It is not necessary to supply the water 23 from the water supply unit 24 as shown in FIG.

Thus, according to the CO ₂ recovery apparatus 10C according to the present embodiment, the inorganic main component is obtained by adding the organic oxidant 31 to the oxidation treatment tank 32 arranged on the downstream side of the sulfuric acid supply unit 22. The organic waste 25 remaining in the solution 19 containing waste can be oxidized. Thereby, even when the organic waste 25 remains in the solution 19 containing the inorganic main waste, the remaining organic waste 25 is removed from the solution 19 containing the inorganic main waste. Can do.

  Further, since the COD value of the solution 19 containing the inorganic main waste in the oxidation treatment tank 32 can be lowered to a predetermined reference value or less, the water supply unit 24 as shown in FIG. 1 is provided. In addition, the COD value of the solution 19 containing the inorganic main waste can be discharged at a predetermined reference value or less.

As described above, in the CO ₂ recovery device and the waste treatment method according to the present invention, the anion exchange unit and the reclaimer are arranged in series, and the inorganic acid and the organic acid in the partially extracted lean solution are ionized. After removal by replacement, organic waste is treated with a reclaimer, enabling separation of organic waste and inorganic-based waste, and reducing the amount of waste processed in the waste incinerator. It is suitable for use in the treatment of mixed waste in the lean solution of the intended CO ₂ recovery unit.

It is a schematic diagram of a CO ₂ recovery apparatus according to a first embodiment of the present invention. It is a schematic diagram of a CO ₂ recovery apparatus according to a second embodiment of the present invention. It is a schematic diagram of a CO ₂ recovery apparatus according to a third embodiment of the present invention. It is a schematic view of a conventional CO ₂ recovery apparatus. It is a schematic view of another conventional CO ₂ recovery apparatus.

10A to 10C CO ₂ recovery device 11 Lean solution extraction line 12 Solid-liquid separation unit 13 Anion exchange unit 14 First recycling line 15 Turbidimeter 16 Second recycling line 17 Sodium hydroxide aqueous solution 18 Alkaline solution supply unit 19 Inorganic Solution containing system waste 20 Inorganic system waste line 21 Sulfuric acid (H ₂ SO ₄ )
22 Sulfuric Acid Supply Unit 23 Water 24 Water Supply Unit 25 Organic Waste 26 Organic Waste Discharge Line 27 Waste Incinerator 30 Organic Oxidant Supply Unit 31 Organic Oxidant 32 Oxidation Treatment Tank 1005 CO ₂ Absorbent 1006 Absorption Tower 1007 Rich solution 1008 Regeneration tower 1009 Lean solution 1022 Lean solution supply line 1040-1 First reclaimer 1040-2 Second reclaimer

Claims (14)

Removal and absorption tower in which the gas contacting the the CO ₂ absorbing solution for removing CO _2, and regeneration tower plays the rich solution that has absorbed CO ₂ to the heat exchange, the CO ₂ in the regeneration tower containing CO ₂ A CO ₂ recovery device for reusing the lean solution in the absorption tower,
A lean solution extraction line for extracting a part of the lean solution produced in the regeneration tower;
An anion exchange unit that removes the inorganic acid and the organic acid in the lean solution extracted in the lean solution extraction line by ion exchange;
The lean solution, which is provided on the downstream side of the anion exchange unit and from which the inorganic acid and organic acid have been removed in the anion exchange unit, is heated to evaporate the CO ₂ absorbing solution remaining in the lean solution . A first reclaimer for ,
A vaporized CO ₂ absorbing liquid feed line for supplying the CO ₂ absorbing liquid vaporized by the first reclaimer to the bottom side of the regeneration tower ;
Organic waste discharge for extracting neutral organic compounds and basic organic compounds in the lean solution from which inorganic acids and organic acids have been removed by the first reclaimer as organic waste from the first reclaimer Line,
An alkaline solution supply unit for supplying an alkaline agent to the anion exchange unit;
An inorganic main waste discharge line for separating the anion exchange resin from the anion exchange resin by the alkali agent and using the inorganic acid and organic acid eluted in the solution as the inorganic main waste, and discharging the solution containing the inorganic main waste. When,
A CO ₂ recovery device characterized by comprising: In claim 1,
A solid-liquid separation unit is provided on the upstream side of the anion exchange unit and separates solids remaining in the lean solution extracted in the lean solution extraction line. CO ₂ recovery device. In claim 1 or 2,
A CO ₂ recovery device comprising a first recycle line for returning the lean solution from which solid matter has been removed in the solid-liquid separation unit to the upstream side of the solid-liquid separation unit. In any one of Claims 1 thru | or 3,
A second recycle line is provided for returning the lean solution from which the inorganic acid and the organic acid have been removed in the anion exchange part between the solid-liquid separation part and the anion exchange part. CO ₂ recovery device. In claim 1 or 2 ,
The solution containing the inorganic metallic wastes separated by the alkali agent is supplied to the anion-exchange unit from the alkaline solution supply unit, and characterized by having a sulfuric acid supply unit for supplying the sulfuric acid CO ₂ recovery device. In claim 5 ,
A CO ₂ recovery device comprising a water supply unit for supplying water to a solution containing inorganic main waste supplied with sulfuric acid. In claim 6 ,
Provided in the inorganic main waste discharge line between the sulfuric acid supply unit and the water supply unit;
A CO ₂ recovery apparatus comprising a second reclaimer for removing organic waste remaining in a solution containing inorganic main waste supplied with sulfuric acid. In claim 5 ,
Provided on the downstream side of the sulfuric acid supply unit,
It has an oxidation treatment tank for oxidizing the organic waste remaining in the solution containing the inorganic main waste supplied with the sulfuric acid with the organic oxidant supplied from the organic oxidant supply unit. Characteristic CO ₂ recovery device. In any one of Claims 1 thru | or 8 ,
A heat exchanger for exchanging heat between the rich solution and the lean solution, the heat exchanger, and the absorption tower immediately before the absorption tower is located at a position where a part of the lean solution is extracted from the lean solution extraction line. A CO ₂ recovery device, which is either between a cooler provided between the heat exchanger and the regeneration tower or between the heat exchanger and the regeneration tower. In any one of Claims 1 thru | or 9 ,
Between the solid-liquid separation part and the anion exchange part, a turbidimeter for measuring a turbidity degree in the lean solution from which the solid matter has been removed in the solid-liquid part separation part is provided. CO ₂ recovery equipment. The gas and the CO ₂ absorbing liquid containing CO ₂ into contact in the absorption tower to remove CO _2, and regeneration in regenerator rich solution that has absorbed CO ₂ by heat exchange, removal of CO ₂ in the regeneration tower A waste treatment method in a CO ₂ recovery device for reusing the lean solution in the absorption tower,
A part of the lean solution is extracted to a lean solution extraction line, the lean solution is fed to the anion exchange unit, and the anion exchange resin filled in the anion exchange unit is used in the extracted lean solution. Removing inorganic and organic acids by ion exchange;
The lean solution from which the inorganic acid and organic acid have been removed is fed to the first reclaimer, and the lean solution from which the inorganic acid and organic acid have been removed is heated in the anion exchange unit using the first reclaimer. Evaporating the CO ₂ absorbent remaining in the lean solution ,
The CO ₂ absorption liquid vaporized by the first reclaimer is supplied to the tower bottom side of the regeneration tower via a vaporized CO ₂ absorption liquid supply line, and the CO ₂ absorption liquid is recovered in the regeneration tower.
The neutral organic compound and the basic organic compound in the lean solution from which the inorganic acid and organic acid have been removed by the first reclaimer are used as organic waste as organic waste from the first reclaimer via the organic waste discharge line. the organic waste is removed by extracting Te,
When regenerating the anion exchange resin filled in the anion exchange part, an alkaline agent is added to the anion exchange part, and the inorganic acid adhered and ion exchanged on the anion exchange resin and An organic acid is separated from the anion exchange resin, and the inorganic acid and the organic acid eluted into the solution as a salt of the inorganic acid and the organic acid are used as an inorganic main waste, and the solution containing the inorganic main waste is obtained. A waste treatment method in a CO ₂ recovery apparatus, wherein the pH is adjusted by adding sulfuric acid, diluted with water, and released as a reference value or less . In claim 11 ,
Before the inorganic acid and organic acid in the lean solution from which a part of the lean solution has been extracted is removed by ion exchange, the solid matter remaining in the lean solution is separated into solid and liquid in advance and removed. A waste treatment method in a CO ₂ recovery device . In claim 11 or 12 ,
Adding an alkali agent to the anion exchange part, the solution containing the inorganic metallic wastes, the pH was prepared by adding sulfuric acid in a solution with a second reclaimer comprising the inorganic main waste A waste treatment method in a CO ₂ recovery device , further comprising removing organic waste remaining in the waste water. In claim 12 or 13 ,
Adding an alkali agent to the anion exchange part, the solution containing the inorganic metallic wastes, the pH was prepared by adding sulfuric acid, after accumulated a predetermined amount in the oxidation processing tank, organic matter in the oxidation treatment tank the oxidizing agent is added, the organic waste remaining in the solution containing the inorganic metallic waste oxidation treatment, further waste treatment method in the CO ₂ recovery apparatus, and removing.

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