Process for removal of water from a CO2 containing raw material mixed gas and apparatus therefor

Abstract: In a process for recovery of CO₂ gas from a raw material mixed gas in which the CO₂ is recovered by absorption followed by vacuum desorption, water in the raw material mixed gas is removed by cooling the raw material mixed gas and passing it through a rotary dehumidification apparatus having a dehumidification chamber in which water in the raw material mixed gas is removed by a desiccant, and a regeneration chamber in which water is removed from the desiccant by heating the desiccant. Unadsorbed gas discharged from the CO₂ removal apparatus is heated and then used to heat the desiccant in the regeneration chamber.

Description: The present invention relates to a process for preventing water from accumulating in an adsorbent used in PSA CO₂-recovery method by firstly removing water according to a two-stage process of cooling dehumidification and adsorbing dehumidification. Recovery of CO₂ gas is from a hot-blast stove exhaust gas, combustion exhaust gas or the like which contains water. As an adsorbent used in CO₂ gas separation and recovery by PSA method, carbon molecular sieves, zeolite molecular sieves, activated charcoal and the like are known. However, generally, when water is accumulated in an adsorbent, in addition to decrease in the amount of adsorbed CO₂ gas and the separation capacity, various problems such as powdering of the adsorbent and the like are caused, which results in difficulty in recovery of CO₂ gas in high yield and high purity. Then, many attempts for removal of water in a raw material mixed gas have been proposed. For example, JP-A 62-136222 proposes a process wherein a gas cooler or refrigerating dryer or the like is used as a dehumidification apparatus in order to bring an amount of water in a combustion exhaust gas to a degree of not higher than 20°C as reduced in terms of the dew point. Also, JP-A 1-172204 proposes a process for preventing water from accumulating in a zeolite molecular sieves adsorbent wherein alumina gel as a desiccant is packed at a lower part of the zeolite molecular sieves adsorbent, that is, at the raw material mixed gas inlet side, water in a raw material combustion exhaust gas is removed with this desiccant and then CO₂ gas separation is carried out at the upper part of the zeolite molecular sieves adsorbent. On the other hand, as another process for removal of water, JP-A 1-108106 proposes a process wherein water in a raw material mixed gas is removed by pre-treating the raw material mixed gas according to a PSA method using a synthesized zeolite as an adsorbent before it is fed into a PSA apparatus. Since the above-described various adsorbents, in particular, zeolite molecular sieves have especially high adsorbability of water and the water once adsorbed is difficult to be desorbed, water tends to accumulate in the adsorbent. Therefore, in the case of zeolite molecular sieves, more attention must be paid to the prevention of water accumulation. In order to solve this problem, the above-described JP-A 1-108106 discloses a process wherein PSA for the removal of water is provided as the pretreatment in addition to a CO₂ gas PSA main apparatus. However, in this process, it is unavoidable that the plant cost becomes higher, the operation procedures becomes complicated and the running cost also becomes higher. Although the process described in JP-A 1-172204 uses alumina gel as a desiccant, the desiccant must be used in a large amount. Further, since the regeneration of the alumina gel which has absorbed water is carried out with a desorbed gas (CO₂ gas), the desorbed CO₂ gas is consequently accompanied with water in a raw material mixed gas. Therefore, it is necessary to provide a vacuum pump for desorption having considerably larger capacity to bring a gas corresponding to CO₂ gas and water vapor to evacuate. Furthermore, since much water drain is formed in CO₂ gas recovery lines following the vacuum pump, corrosion-resistant materials are required in order to prevent corrosion. Furthermore, since the drying of CO₂ gas per se is required, there is a problem in that a dehumidification apparatus is also required as a post-treatment process. Accordingly, in a process for separation of CO₂ gas by PSA method using zeolite molecular sieves as a adsorbent, for example, in the case where CO₂ gas is recovered from a mixed gas containing water such as a hot blast stove exhaust gas, combustion exhaust gas or the like, it is desired to develop an excellent process for removal of water in the mixed gas while minimizing the above-described problems. In addition, a process for recovering CO₂ gas in an exhaust gas as high purity CO₂ using the exhaust gas as a raw material gas is a desirable technique from the viewpoint of prevention of the green house effect upon the earth, which has been of recent concern. The essential features of the invention are relayed in claims 1 and 4. The present invention provides a process for removal of water in a raw material mixed gas by which it is possible to minimize the above-described problems. The invention will be described in more detail below with reference to the accompanying drawing (Fig. 1), which is a flow sheet showing one embodiment of the process of the present invention. We have conducted intensive investigations in order to develop an improved process for removal of water in a mixed gas to be used as a raw material in PSA method, and found out that the use of a rotary dehumidification apparatus is effective. A rotary dehumidification apparatus is known [Kagakusochi (Chemical Apparatus), 1989, August, pages 54 to 59]. It has a rotor having a gas permeable structure such as a honeycomb structure or the like and containing as a main desiccant lithium chloride, silica gel or the like. The rotor rotates in a casing which is separated into a treating (dehumidifying) zone and a regeneration zone. Water in a raw material mixed gas to be treated is removed by silica gel or the like which is bound to the honeycomb in the rotor during passing through therein and the gas is discharged in the dried state from an outlet. On the other hand, the honeycomb which has adsorbed water moves to the regeneration zone by the rotation of the rotor and the honeycomb is regenerated into the dried state by evaporation and desorption of water adsorbed therein with an inflow heated gas. Then, the honeycomb moves to the treating zone again by the rotation. The process of the present invention can be applied to PSA method using a raw material mixed gas containing 5 to 80 v/v% of CO₂ gas such as a hot-blast stove exhaust gas, a combustion exhaust gas or the like. In the process of the present invention, an unadsorbed gas which is discharged from a PSA apparatus is heated to use as a hot gas for regeneration in the above-described dehumidification apparatus. The unadsorbed gas which has passed through an adsorbent packed layer in the adsorber is in the dried state as a matter of course, an amount of water in the gas is very small such that it has a dew point of -50 to -70°C and, therefore, when the gas is heated, a bone dried state gas can be obtained. When this gas is used as a heated gas for regeneration, extremely superior regeneration effects can be obtained in comparison with conventional processes wherein a merely heated gas is used. The heating method of the above unadsorbed gas is not limited. For example, when a hot-blast stove exhaust gas, a combustion exhaust gas or the like is used as a raw material gas, in view of energy saving or process system, it is significantly advantageous to carry out the heating by heat exchange between the exhaust gas and the unadsorbed gas. Further, in the process of the present invention, an adsorbed gas (CO₂ gas) which has been desorbed in PSA operations is sucked in a direction opposite to that of introduction of the raw material mixed gas to use for drying the adsorbents at a raw material mixed gas inlet side part. That is, even if the above-described rotary dehumidification apparatus is used to remove water in the raw material mixed gas, the trace of water remains and this water is gradually accumulated in adsorbents in a raw material mixed gas inlet side part. In particular, when zeolite molecular sieves are used as an adsorbent to recover CO₂ gas from a raw material mixed gas, since water is adsorbed more strongly than CO₂ gas, a part where adsorption of water is remarkable is formed at a raw material mixed gas inlet side upon termination of the adsorption step. Therefore, in this case, when an adsorbed CO₂ gas is desorbed by a vacuum pump, the suction is carried out in the direction opposite to that of introduction of the raw material mixed gas and the adsorbent is rinsed and dried with the dried CO₂ gas. Thus, water adsorbed to the adsorbent in a trace amount at a raw material mixed gas inlet side part in the adsorption step is rinsed and removed in the desorbing step. Since water in the desorbed CO₂ gas is negligible, further dehumidification is not required and the resultant gas per se can be used as a product gas. An embodiment of the process of the present invention is illustrated below with reference to the accompanying Fig. 1. In this embodiment, CO₂ is recovered from a hot-blast stove exhaust gas. A hot-blast stove exhaust gas is introduced from an exhaust gas inlet 1 into a PSA apparatus 5 by an exhaust gas feed blower 4 via an exhaust gas-unadsorbed gas heat exchanger 2 and a scrubber 3. An unadsorbed gas which is heated by the heat exchanger 2 is introduced into a regeneration zone of a rotary dehumidification apparatus 6 and this is used to remove water adsorbed to a rotor of the dehumidification apparatus 6. On the other hand, in the scrubber 3, an exhaust gas is subjected to the removal of dusts which are contained therein in a small amount and to cooling. Since the gas discharged from the exhaust gas feed blower 4 is in the wet state, the gas is cooled and dehumidified by cooling means, provided by a cooler 7 with cooling water at ambient temperature and then a cooler 8 with chilled water. Then, the gas is introduced into a dehumidifying zone of rotary dehumidification apparatus 6. The temperature of the exhaust gas after cooling and dehumidification with chilled water is suitably 0 to 15°C. When the temperature is lower than 0°C, water in the exhaust gas is frozen and it is not preferable. On the other hand, when the temperature exceeds 15°C, the regeneration temperature must be raised due to increase in the water load in the rotary dehumidification apparatus 6 and, when the high temperature exhaust gas is introduced in a PSA apparatus packed with zeolite molecular sieves, the separation is affected adversely. Thus, by setting a temperature within the above-described range, the temperature of the exhaust gas discharged from the rotary dehumidification apparatus 6 becomes 20 to 50°C which is a suitable temperature range for PSA operations in the PSA apparatus 5, which makes the effective CO₂ separation and recovery possible. After adsorption and dehumidification in the apparatus 6, water in the exhaust gas is reduced to a degree corresponding to a dew point of -45 to -50°C. The gas from which water has been thus removed is introduced into the PSA apparatus 5 through a raw material mixed gas inlet valve 9 and the adsorption step is carried out. A part of the unadsorbed gas which is discharged at the adsorption step is fed into the above-described heat exchanger 2 by a regeneration blower 10 to heat it. Since heating is carried out by the raw material mixed gas, i.e., the hot-blast stove exhaust gas, the temperature of the unadsorbed gas becomes 125 to 140°C at a heat exchanger outlet and this temperature is sufficient for regeneration in the dehumidification apparatus 6. An unadsorbed gas which has not been used for heating is discharged from an unadsorbed gas outlet 14. Then, the desorption of the adsorbed CO₂ gas by a vacuum pump 11 and the regeneration of the adsorbent are carried out simultaneously. The desorption of CO₂ gas is carried out by suction in the direction opposite to introduction of the raw material mixed gas through a CO₂ gas outlet valve 12 using the vacuum pump 11 as described above. CO₂ gas thus obtained is stored in a CO₂ tank 13. In this embodiment, there is only adsorber in the PSA apparatus 5. However, likewise, water in the exhaust gas can be removed by using a plurality of adsorbers by similar operations. The present invention can be sufficiently applied not only to a zeolite molecular sieves adsorbent but also to an activated charcoal adsorbent. According to the present invention, a significant accumulation of water in an adsorbent is not observed and the lowering of capacity of expensive adsorbents by water adsorption can be avoided. Therefore, the following advantages are obtained. 1) Since a product gas is obtained in the dried state, an apparatus for dehumidification of the product as in a conventional facility is not required and, therefore, the plant initial cost and the running cost are remarkably saved. 2) Since no water drain occurs in product gas lines, there is no need to use corrosion-resistant materials in pipings and tanks and the plant initial cost can be reduced. 3) Since the inclusion of water in a product gas line is scarce, the capacity of a vacuum pump which is installed in a PSA apparatus can be reduced. Power of this vacuum pump occupies the majority of that of CO₂ gas recovery and, therefore, significant decrease in electric power for CO₂ gas recovery is attained. The following Example further illustrates the present invention in more detail. Example 1 The removal of water in a raw material mixed gas was carried out using a PSA apparatus similar to that of Fig. 1, but equipped with three adsorbers. A hot-blast stove exhaust gas (temperature: 200 to 250°C, composition: CO₂ gas 23%, N₂ gas 70%, O₂ gas 2%, water 5%) was used as a raw material mixed gas, this was supplied to a scrubber at 22000 Nm³/hour via a heat exchanger and, the cooling of the raw material mixed gas and the removal of dusts which were contained therein in a small amount were carried out, simultaneously. The temperature of the gas which was discharged from the scrubber became 50 to 60°C. This gas was cooled and dehumidified by cooling water (ambient temperature) and chilled water (5 to 10°C) to bring the temperature of the gas to about 10°C, and adsorbed and dehumidified by a rotary dehumidification apparatus (SSCR dehumidifier manufactured by Seibu Giken Co., Ltd., Japan) having a rotor composed of a combined body of honeycomb-like activated silica gel to remove water to a degree corresponding to a dew point of -45 to -50°C. As a gas for regeneration in the rotary dehumidification apparatus, 7000 Nm³/hour of a PSA unadsorbed gas was used and it was subjected to heat exchange with the hot-blast stove exhausted gas at the above-described temperature to heat to 125 to 140°C. As a result, the temperature of the gas from which water had been removed became 35 to 40°C at an outlet of the rotary dehumidification apparatus, and this gas was supplied to a PSA apparatus having three adsorbers of 2.8 m⊘ in inner diameter and 10 m in length which were packed with zeolite molecular sieves. At this time, in the desorption step, the suction was carried out in the direction opposite to gas introduction at the adsorption step using a vacuum pump (ultimate pressure: 30 to 60 torr) to obtain a product gas. The product CO₂ gas was obtained at the flow rate of 2900 Nm³/hour. CO₂ purity was 99% and it was in the dried state of -30 to -40°C as reduced in terms of its dew point. The yield was 56.7%.

Claims: A process for recovery of CO₂ gas from a raw material mixed gas containing 5 to 80 v/v% of CO₂ gas by pressure swing gas adsorption and separation, characterized in that removal of water in the raw material mixed gas is carried out by cooling the raw material mixed gas and passing it through a rotary dehumidification apparatus to remove water in the raw material mixed gas, and the regeneration of the rotary dehumidification apparatus is carried out by heating unadsorbed gas discharged from an adsorption step in PSA and using the heated gas for regeneration, the dehumidification and regeneration steps being carried out simultaneously. A process according to claim 1, wherein the temperature of the raw material mixed gas after removal of water in the mixed gas by cooling is 0 to 15°C. A process according to claim 1 or 2, wherein CO₂ gas obtained by desorption in a desorption step in PSA method is sucked in a direction opposite to the flow of the introduced raw material mixed gas so as to remove water in an adsorbent packed region adjacent to a raw material mixed gas inlet of the PSA apparatus. An apparatus for recovery of CO₂ from a mixture of gases containing CO₂ and water, which apparatus comprises cooling means (7,8) for dehumidifying the mixture of gases, a rotary dehumidification apparatus (6) comprising a dehumidification chamber, a regeneration chamber and a mass of desiccant material, which mass of desiccant material is rotatable between a first position in which a first part of the mass is present in the dehumidification chamber and a second part of the mass is in the regeneration chamber, and a second position in which the first part of the mass is in the regeneration chamber and the second part of the mass is in the dehumidification chamber, means (4) for feeding the mixture of gases containing CO₂ and water through cooling means (7,8) into the dehumidification chamber of the dehumidification apparatus (6) for contact of the mixture of gases with the said desiccant material in the chamber to remove the water from the mixture of gases by adsorption of the water onto the desiccant, an adsorption chamber (5) containing an adsorbant material for adsorbing CO₂ from the gaseous mixture received from the rotary dehumidification apparatus (6), means (11) for reducing the pressure in the adsorption chamber (5) to desorb the CO₂ from the adsorbant material, means (2) for heating unadsorbed gas discharging from the adsorption chamber, and means for directing the heated unadsorbed gas from the adsorption chamber to the regeneration chamber to effect regeneration of the desiccant material therein, thereby removing water therefrom.

Inventors: ARAI FUMIO C O NKK CORPORATION, MATSUZAKI KENJI C O NKK CORPOR, SEKIKAWA NORIO C O ADCHEMCO CO, UNO MASARU C O SUMITOMO SEIKA, YAMAGUCHI AKIRA C O SUMITOMO S, ARAI, FUMIO, C/O NKK CORPORATION, MATSUZAKI, KENJI, C/O NKK CORPORATION, SEKIKAWA, NORIO, C/O ADCHEMCO CORPORATION, UNO, MASARU, C/O SUMITOMO SEIKA, YAMAGUCHI, AKIRA, C/O SUMITOMO SEIKA
Applicants: SUMITOMO SEIKA CHEMICALS, SUMITOMO SEIKA CHEMICALS CO., LTD.
Application year: 1991
Main classification: B01D53
IPC codes: C01B31, B01D53