JPH01290517A - Method and apparatus for raw gas treatment in high purity liquified co2 plant - Google Patents
Method and apparatus for raw gas treatment in high purity liquified co2 plantInfo
- Publication number
- JPH01290517A JPH01290517A JP63122892A JP12289288A JPH01290517A JP H01290517 A JPH01290517 A JP H01290517A JP 63122892 A JP63122892 A JP 63122892A JP 12289288 A JP12289288 A JP 12289288A JP H01290517 A JPH01290517 A JP H01290517A
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- gas
- gaseous
- adsorption tower
- dehumidifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 133
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 63
- 239000001569 carbon dioxide Substances 0.000 claims description 60
- 238000000746 purification Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 11
- 230000001877 deodorizing effect Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 235000011089 carbon dioxide Nutrition 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 65
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 238000007791 dehumidification Methods 0.000 abstract 1
- 239000003863 metallic catalyst Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- WLFVAZPWBVBENV-UHFFFAOYSA-N [K].[K].[K].[K].[K] Chemical compound [K].[K].[K].[K].[K] WLFVAZPWBVBENV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Drying Of Gases (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ボイラー排ガス等を原料ガスとしてこれから
高純度液化炭酸を製造する方法及び装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method and apparatus for producing high-purity liquefied carbonic acid from boiler exhaust gas or the like as a raw material gas.
食品工業分野で使用される液化炭酸は、アンモニア合成
プラント、酸化エチレンプラント等から発生するオフガ
スを原料とし、第３図に示した設備を使用して製造され
ている（昭和６１年２月１日株式会社フジ・テクノシス
テム発行「副生ガス及び合成ガスを中心としたガス分離
・精製とその利用技術」第５９〜６２頁）。Liquefied carbonic acid used in the food industry is produced using off-gas generated from ammonia synthesis plants, ethylene oxide plants, etc., using the equipment shown in Figure 3 (February 1, 1986). "Gas separation/purification and its utilization technology focusing on by-product gas and synthesis gas" published by Fuji Techno System Co., Ltd., pp. 59-62).
たとえば、アンモニア合成プラント３１で発生した原料
ガス３２を、炭酸ガス吸収塔３３を通過させて原料ガス
３２に含まれている炭酸ガスをアルカリｉに吸収させる
。吸収された炭酸ガスは、アルカリ液を減圧、スチーム
加熱することによって、純度９０％以上の組成炭酸ガス
３４として分離される。For example, the raw material gas 32 generated in the ammonia synthesis plant 31 is passed through the carbon dioxide absorption tower 33, and the carbon dioxide contained in the raw material gas 32 is absorbed by the alkali i. The absorbed carbon dioxide gas is separated as carbon dioxide gas 34 having a purity of 90% or more by reducing the pressure of the alkaline solution and heating it with steam.
組成炭酸ガス３４は、第１表に示すように少量の不純物
を含むものである。そして、食品工業用に使用される炭
酸ガスは、同表に示すレベルを満足するまで不純物を低
下させることが食品衛生法上から要求される。そこで、
組成炭酸ガス３４を洗浄塔３５．コンプレッサー３６．
脱湿器３７．脱臭塔３８に流して予備処理し、液化精製
装置３９で純度９９．９％以上の炭酸ガスに精製してい
る。なお、第１表における痕跡ｆｉ ｔ ｒ 、 は
、食品衛生法で規定された分析法により検出されないレ
ベルをいう。The composition of the carbon dioxide gas 34 contains a small amount of impurities as shown in Table 1. According to the Food Sanitation Law, carbon dioxide gas used in the food industry is required to reduce its impurities to the level shown in the same table. Therefore,
The composition carbon dioxide gas 34 is sent to a cleaning tower 35. Compressor 36.
Dehumidifier 37. It is passed to a deodorizing tower 38 for pretreatment, and then purified to a carbon dioxide gas with a purity of 99.9% or more in a liquefaction purification device 39. Note that the trace fi tr in Table 1 refers to a level that is not detected by the analysis method specified in the Food Sanitation Act.
第 １ 表
また、最近では、前掲した文献にも紹介されているよう
に、原料ガス３２として、製鉄所で副生じた転炉ガス（
ＬＤＧ）、高炉ガス（Ｂ Ｆ Ｇ）、コークス炉ガス（
ＣＯＧ）、石灰炉ガス等から圧力スイング吸着法によっ
て炭酸ガスを回収し、予備処理した後で液化精製する方
法も確立されている。Table 1 In addition, recently, as introduced in the above-mentioned literature, converter gas (as a by-product in steel works) has been used as raw material gas32.
LDG), blast furnace gas (BFG), coke oven gas (
A method has also been established in which carbon dioxide gas is recovered from lime furnace gas (COG), lime furnace gas, etc. by a pressure swing adsorption method, and is pretreated and then liquefied and purified.
この場合、アンモニア合成プラントや酸化エチレンプラ
ント等で発生したガスと異なり、窒素酸化物ＮＯが原料
ガスに含まれている。Ｎｏは、吸着剤に対する吸着性が
低く、また水に対する溶解度も高くないために、脱臭塔
３８や洗浄塔３５で除去することが困難である。しかも
、このＮｏは、液化精製装置３９で残留０２と反応して
ＮＯ２となり、液相側に移行して、精製された炭酸ガス
の品質を下げる原因にもなる。In this case, unlike gases generated in ammonia synthesis plants, ethylene oxide plants, etc., nitrogen oxide NO is contained in the raw material gas. Since No has low adsorption to an adsorbent and does not have high solubility in water, it is difficult to remove it in the deodorizing tower 38 or the cleaning tower 35. Moreover, this No reacts with residual O2 in the liquefaction purification device 39 to become NO2, which moves to the liquid phase side and becomes a cause of lowering the quality of the purified carbon dioxide gas.
そこで、Ｋ Ｍ ｎ ０４を使用してＮＯをＫＮＯ３と
しぞ固定することによって、炭酸ガスから分離する方法
（以下、これをＫＭｎＯ，法という）が−船釣に採用さ
れている。Therefore, a method of separating NO from carbon dioxide by fixing NO as KNO3 using KMn04 (hereinafter referred to as the KMnO method) has been adopted for boat fishing.
ところが、ＫＭｎＯ，法は、固形のＫＭｎＯ，をアルカ
リに溶解して、炭酸ガス吸収塔に送り込むため、複雑な
設備が必要となる。また、ＮＯを吸収した後のアルカリ
からＫ Ｎ Ｏ３を除去するフィルターブレス等の濾過
装置や、廃液に対する処理設備も要求される。そのため
、設備費、用役費に対する負担が大きく、またメンテナ
ンスも複雑になる。However, the KMnO method requires complicated equipment because solid KMnO is dissolved in an alkali and sent to a carbon dioxide absorption tower. Additionally, a filtration device such as a filter breath that removes K N O3 from the alkali after absorbing NO and treatment equipment for waste liquid are also required. Therefore, the burden on equipment costs and utility costs is large, and maintenance becomes complicated.
そこで、本発明は、組成炭酸ガスに含まれている０２を
予め除去する脱酸素設備を脱湿器の上流側に設けること
により、複雑な工程を必要とするＫ Ｍ ｎ ＯＩ法に
よらずに、液化精製装置に送り込まれる炭酸ガス中の酸
素含有１を下げ、薄化精製装置でＮＯ２となって液相側
に移行する窒素酸化物の量を減少させ、精製される炭酸
ガスの品質を向上させることを目的とする。Therefore, the present invention eliminates the need for the KM n OI method, which requires a complicated process, by providing a deoxidizing equipment upstream of the dehumidifier to remove 02 contained in the carbon dioxide composition in advance. , lowers the oxygen content 1 in the carbon dioxide gas sent to the liquefaction purification device, reduces the amount of nitrogen oxides that become NO2 in the thinning purification device and transfers to the liquid phase side, and improves the quality of the purified carbon dioxide gas. The purpose is to
本発明の処理方法は、その目的を達成するために、少な
くともＣ０２及びＮＯを含有するガスを炭酸ガス吸着塔
で処理して組成炭酸ガスとした後で、液化ｗＩ製装冒で
液化炭酸にする工程に先立って、前記組成炭酸ガスを脱
酸素した後、水蒸気を除去することを特徴とする。In order to achieve the objective, the treatment method of the present invention processes a gas containing at least CO2 and NO in a carbon dioxide gas adsorption tower to convert it into composition carbon dioxide gas, and then converts it into liquefied carbon dioxide in a liquefaction wI equipment. Prior to this process, the carbon dioxide composition is deoxidized and then water vapor is removed.
また、この方法を実施するための装置は、少な（ともＣ
０２及びＮｏを含有するガスから組成炭酸ガスを得る炭
酸ガス吸着塔と液化精製装置との間に、工程順にコンプ
レッサー、脱酸素装蜜、脱湿器及び脱臭塔を配列したこ
とを特徴とする。In addition, the equipment for carrying out this method is small (and C
The present invention is characterized in that a compressor, a deoxidizer, a dehumidifier, and a deodorizing tower are arranged in the order of steps between a carbon dioxide gas adsorption tower that obtains compositional carbon dioxide from gas containing No. 02 and No. 02 and a liquefaction purification device.
ボイラー排ガス等の原料ガスは、目標成分としてのｃｏ
２の外に、Ｎ２． Ｎ Ｏ，Ｎ Ｏ２，Ｈ−０，Ｓ Ｏ
２゜Ｈ２Ｓ、 Ｏ，、ＣＯ等の不純物を含んでいる。こ
れら各不純物は、たとえば活性炭等の吸着剤に対して、
次の順のように吸着性に差がある。Raw material gas such as boiler exhaust gas contains CO as a target component.
In addition to 2, N2. N O, N O2, H-0, S O
Contains impurities such as 2°H2S, O, and CO. For example, each of these impurities is
There are differences in adsorption properties in the following order:
Ｎ２．０２． Ｎ Ｏ，ＣＯ＜ Ｃ０２＜ Ｈ２Ｏ，Ｓ
０２． Ｈ２Ｓ、 ＮＯ２ま゛た、各不純物の沸点も
、この順位に従って高くなる。そこで、予備処理された
炭酸ガスを液化精製装置で精製するとき、残留するＮＯ
２は、吸収液側に残留し、液化炭酸に不純物として移行
する。他方、ＮＯは、低沸点のために精製液に吸収され
ずに、放出される。N2.02. NO, CO<C02< H2O, S
02. The boiling points of impurities such as H2S and NO2 also increase in this order. Therefore, when pre-treated carbon dioxide is purified using a liquefaction purifier, the remaining NO
2 remains on the absorption liquid side and transfers to liquefied carbonic acid as an impurity. On the other hand, NO is not absorbed into the purified liquid due to its low boiling point, but is released.
ところが、本発明者等の研究によると、脱臭塔から送ら
れて来た炭酸ガスに０２が含まれているとき、液化精製
装置においてＮｏがＮ Ｏ２に酸化され、精製液に吸収
され易くなり、その結果精製された炭酸ガスの純度が低
下することが判った。However, according to research by the present inventors, when the carbon dioxide gas sent from the deodorizing tower contains 02, No is oxidized to NO2 in the liquefaction purification equipment and easily absorbed into the purified liquid. As a result, it was found that the purity of the purified carbon dioxide gas decreased.
そこで、本発明においては、組成炭酸ガスに含まれてい
る０２ を脱酸素装置で水蒸気に変え、この水蒸気を脱
湿器で除去することによって、前述した○、による影響
、すなわちＮ○→Ｎ Ｏ２の反応を抑制し、純度の高い
炭酸ガスを製造するものである。Therefore, in the present invention, by converting the 02 contained in the composition carbon dioxide into water vapor using a deoxidizer and removing this water vapor using a dehumidifier, the influence of ○ mentioned above, that is, N○ → NO2 This suppresses the reaction of carbon dioxide and produces carbon dioxide gas with high purity.
なお、本発明において使用される原料ガスは、炭酸ガス
を含んでいる限り、各種のガスが使用される。たとえば
、転炉ガス（ＬＤＧ）、高炉ガス（ＢＦ Ｇ）、コーク
ス炉ガス（ＣＯＧ）、石灰炉ガス等の、排熱をスチーム
として回収した後の、ボイラー排ガスを使用することも
できる。Note that various gases can be used as the raw material gas used in the present invention as long as they contain carbon dioxide gas. For example, it is also possible to use boiler exhaust gas, such as converter gas (LDG), blast furnace gas (BFG), coke oven gas (COG), lime furnace gas, after the exhaust heat is recovered as steam.
以下、図面を参照しながら、実施例により本発明のｖＦ
＠を具体的に説明する。Hereinafter, with reference to the drawings, the vF of the present invention will be described by way of example.
Let me explain @ in detail.
ＬＤＧボイラー１で発生した原料ガス２から、炭酸ガス
吸着塔３で炭酸ガスが吸着分離される。Carbon dioxide gas is adsorbed and separated from the raw material gas 2 generated in the LDG boiler 1 in the carbon dioxide adsorption tower 3 .
この炭酸ガス吸着塔３としては、たとえば圧力を周期的
に変動させて吸着及び脱着を行うものが使用される。吸
着分離された炭酸ガスは、組成炭酸ガス４として炭酸ガ
ス吸Ｍ塔３から放出され、コンプレッサー５で約１５ｋ
ｇ／ｃ＋ｒｌ程度に昇圧された後、触媒が充填された脱
酸素装置６に送り込まれる。As this carbon dioxide gas adsorption tower 3, for example, one that performs adsorption and desorption by periodically varying the pressure is used. The adsorbed and separated carbon dioxide gas is released from the carbon dioxide absorbing tower 3 as a composition carbon dioxide gas 4, and is compressed by a compressor 5 to approximately 15 kg.
After being pressurized to approximately g/c+rl, it is sent to a deoxidizer 6 filled with a catalyst.
脱酸素装置６には、Ｐｔ、 Ｎｉ等の金属触媒が充填
されている。また、別系統の配管から、Ｎ２ が導入さ
れる。したがって、組成炭酸ガス４に含まれている０２
は、金属触媒の作用でＮ２と反応して水蒸気Ｈ，Ｏとな
る。たとえば、粒径２〜４ ｍｍのアルミナをキャリア
とするＰｄ品位１．８±０．２ｇ／Ｌの触媒を充填した
脱酸素装置６に温度４０℃で０２含有量２００ｐｐｍの
組成炭酸ガス４をＳＶ約１０．０００で供給し、脱酸素
装置６の内部を温度４０℃、圧力１５ｋｇ／ｃｌＴｌＧ
に維持し、当量の２〜３倍過剰の流量で温度４０℃のＮ
２ と反応させたところ、脱酸素装置６から排出され
たガスの０２含有量はｉｐｐｍ以下に低下しており、実
質的に全量の０２がＮ２０に変化していた。The deoxidizer 6 is filled with a metal catalyst such as Pt or Ni. In addition, N2 is introduced from another system of piping. Therefore, the 02 contained in the composition carbon dioxide 4
reacts with N2 to form water vapor H and O under the action of a metal catalyst. For example, carbon dioxide gas 4 having a composition of 200 ppm of 02 is heated at a temperature of 40° C. to a deoxidizing device 6 filled with a catalyst having a Pd grade of 1.8±0.2 g/L and using alumina with a particle size of 2 to 4 mm as a carrier. The inside of the deoxidizer 6 is heated at a temperature of 40°C and a pressure of 15 kg/clTlG.
N at a temperature of 40°C with a flow rate of 2-3 times excess of the equivalent amount.
When reacted with 2, the 02 content of the gas discharged from the deoxidizer 6 was reduced to less than ippm, and substantially the entire amount of 02 was changed to N20.
脱酸素装置６としては、たとえば第２図に示すように二
槽式のものを使用することができる。この場合ミ導入配
管６ａ及び導出配管６ｈに設けられている開閉弁５ｂ、
５ｃ及び６ｆ、 ６ｇの切換え操作によって、組成炭
酸ガス及びＮ７を脱酸素槽６ｄ又は６ｅの何れかに導入
する。そして、ガスを導入していない脱酸素槽６ｅ又は
６ｄでは、触媒を賦活させる。そして、所定時間が経過
した後、開閉弁５ｂ、 ５ｃ、 ５ｆ。As the deoxidizing device 6, for example, a two-tank type device as shown in FIG. 2 can be used. In this case, an on-off valve 5b provided in the inlet pipe 6a and the outlet pipe 6h,
By switching between 5c, 6f, and 6g, the composition carbon dioxide and N7 are introduced into either the deoxidizing tank 6d or 6e. Then, in the deoxidizing tank 6e or 6d to which no gas is introduced, the catalyst is activated. After a predetermined period of time has elapsed, the on-off valves 5b, 5c, and 5f are opened.
６ｇを切り換え、賦活された触媒が充填されている脱酸
素装置６ｅ又は６ｄで組成炭酸ガス４を脱酸素する。こ
のようにして、コンプレッサー５から送られてくる組成
炭酸ガス４を連続的に処理することができる。
、脱酸素された炭酸ガス
７は、次いで脱湿器８に導入される。この脱湿器８には
、たとえばシリカゲル等の吸湿剤が充填されている。こ
の脱湿器８では、当初から組成炭酸ガス４に含まれてい
る水蒸気と共に、前述の脱酸素反応で精製した水蒸気も
除去され、脱湿器８を通過したガス９は、大気圧下の露
点−６０℃程度にまで水分除去される。6g, and the carbon dioxide gas 4 is deoxidized in the deoxidizer 6e or 6d filled with an activated catalyst. In this way, the composition carbon dioxide gas 4 sent from the compressor 5 can be continuously processed.
The deoxidized carbon dioxide gas 7 is then introduced into a dehumidifier 8. This dehumidifier 8 is filled with a moisture absorbent such as silica gel. In this dehumidifier 8, the water vapor purified by the above-mentioned deoxidation reaction is removed together with the water vapor contained in the composition carbon dioxide gas 4 from the beginning, and the gas 9 that has passed through the dehumidifier 8 has a dew point under atmospheric pressure. Moisture is removed to about -60°C.
その後、除湿炭酸ガス９は、脱臭塔１０に導入される。Thereafter, the dehumidified carbon dioxide gas 9 is introduced into the deodorizing tower 10.
脱臭塔１０には、たとえば活性炭等の吸着剤が充填され
ており、吸着性の高いＨ，Ｓ、Ｓｏ□。The deodorizing tower 10 is filled with an adsorbent such as activated carbon, which has high adsorption properties for H, S, and So□.
ＮＯ２等が吸着除去される。NO2 etc. are adsorbed and removed.
次いで、脱臭後のガスは、蒸溜分離式の液化精製装置１
１に導入され、冷媒によって約−３０℃まで冷却され、
低温蒸溜塔で蒸溜液化される。このとき、前述した沸点
の差によりＮ２． Ｎｏ等がＣＯ２から分離される。Next, the deodorized gas is passed through a distillation separation type liquefaction purification device 1.
1 and cooled to approximately -30°C by a refrigerant,
It is distilled into liquid in a low-temperature distillation tower. At this time, due to the boiling point difference mentioned above, N2. No. etc. are separated from CO2.
この脱臭塔１０から液化精製装置１１に流れる除湿炭酸
ガス９は、前工程である脱酸素によって０２ のない状
態となっている。そのため、Ｎ Ｏ，Ｏｘ等が濃縮され
易い液化精製装置１１の蒸盾塔頂部で、Ｎｏが酸化され
てＮＯ２となることがない。したがって、液化精製装置
１１から排出された液化炭酸１２は、ＮＯ□含有量の少
ない高品質のものとなる。The dehumidified carbon dioxide gas 9 flowing from the deodorizing tower 10 to the liquefaction purification device 11 has been deoxidized in the previous step and is free of O2. Therefore, NO is not oxidized to NO2 at the top of the steam shield column of the liquefaction purification device 11, where NO, Ox, etc. are likely to be concentrated. Therefore, the liquefied carbonic acid 12 discharged from the liquefaction purification device 11 is of high quality and has a low NO□ content.
次の第２表は、以上に説明した脱酸素の効果を具体的に
表したものである。The following Table 2 specifically shows the effect of oxygen removal explained above.
第 ２ 表
なお、第２表における比較例は、第１図において脱酸素
装置６を設けずに組成炭酸ガス４を予備処理した場合を
示す。この対比から明らかなように、比較例においては
得られた液化炭酸に食品衛生上から望ましくないとされ
ているＮ Ｏ２が５０ｐｐｍ含まれているのに対し、本
実施例の場合には検出できない程度にＮＯ２が除かれて
いる。これは、脱臭塔１０から液化精製装置１１に送り
込まれるガスに酸素が含有されておらず、液化精製装置
１１の蒸溜塔で２ＮＯ＋（Ｌ→ＮＯ２の反応が起こって
いないことを示すものである。Table 2 The comparative example in Table 2 shows the case where the composition carbon dioxide gas 4 was pretreated without providing the deoxidizing device 6 in FIG. 1. As is clear from this comparison, in the comparative example, the obtained liquefied carbonic acid contained 50 ppm of N O2, which is considered undesirable from a food hygiene perspective, whereas in the case of this example, the amount was undetectable. NO2 is removed. This indicates that the gas sent from the deodorizing tower 10 to the liquefaction purification device 11 does not contain oxygen, and that the 2NO+ (L→NO2 reaction) is not occurring in the distillation column of the liquefaction purification device 11.
以上に説明したように、本発明においては、液化精製装
置に送り込む炭酸ガスを、予め脱酸素することによって
、炭酸ガスから分離されたＮＯがＮＣｈ に酸化され液
化炭酸に吸収されることを防いでいる。そのため、得ら
れた液化炭酸は、極めて純度の高い製品となる。しかも
、予備処理工程に脱酸素装置を設けるだけで良いため、
生産性の高い液化炭酸製造プラントが構築される。As explained above, in the present invention, by deoxidizing the carbon dioxide gas sent to the liquefaction purification device in advance, NO separated from the carbon dioxide gas is oxidized to NCh and absorbed into the liquefied carbon dioxide. There is. Therefore, the obtained liquefied carbonic acid is a product with extremely high purity. Moreover, since it is only necessary to provide a deoxidizer in the pretreatment process,
A highly productive liquefied carbon dioxide production plant will be constructed.
第１図は本発明実施例のプロセスを説明するためのブロ
ック図であり、第２図は該プロセスに組み込まれる脱酸
素装置の一例を示す。他方、第３図は、従来の液化炭酸
製造プラントを示すブロック図である。
１：ＬＤＧボイラー ２．３２：原料ガス３；炭
酸ガス吸着塔 ４．３４：組成炭酸ガス５．３６：
コンプレッサー ６：脱酸素装置７：脱酸素後の炭酸
ガス ８．３７：脱湿器９：除湿炭酸ガス １０
．３８：脱臭塔１１：液化精製装置 １２：液化
炭酸３１：アンモニア合成プラント
３３：炭酸ガス吸収塔 ３５：洗浄塔３９：液化ｍ
製装置FIG. 1 is a block diagram for explaining a process according to an embodiment of the present invention, and FIG. 2 shows an example of an oxygen removing device incorporated in the process. On the other hand, FIG. 3 is a block diagram showing a conventional liquefied carbon dioxide production plant. 1: LDG boiler 2.32: Raw material gas 3; Carbon dioxide adsorption tower 4.34: Composition carbon dioxide gas 5.36:
Compressor 6: Deoxidizer 7: Carbon dioxide after deoxygenation 8.37: Dehumidifier 9: Dehumidified carbon dioxide 10
．． 38: Deodorizing tower 11: Liquefaction purification device 12: Liquefied carbonic acid 31: Ammonia synthesis plant 33: Carbon dioxide absorption tower 35: Washing tower 39: Liquefaction m
manufacturing equipment
Claims (1)
ガス吸着塔で処理して組成炭酸ガスとした後、液化精製
装置で液化炭酸にする工程に先立って、前記組成炭酸ガ
スを脱酸素した後、水蒸気を除去することを特徴とする
高純度液化炭酸製造プラントにおける原料ガスの処理方
法。 ２、少なくともＣＯ＿２及びＮＯを含有するガスから組
成炭酸ガスを得る炭酸ガス吸着塔と液化精製装置との間
に、工程順にコンプレッサー、脱酸素装置、脱湿器及び
脱臭塔を配列したことを特徴とする高純度液化炭酸製造
プラントにおける原料ガスの予備処理装置。[Claims] 1. After a gas containing at least CO_2 and NO is treated in a carbon dioxide adsorption tower to produce a compositional carbon dioxide gas, the compositional carbonate gas is converted into a compositional carbonic acid gas prior to the step of converting it into liquefied carbonic acid in a liquefaction purification device. A method for processing raw material gas in a high-purity liquefied carbon dioxide production plant, which comprises removing water vapor after deoxidizing it. 2. A compressor, a deoxidizer, a dehumidifier, and a deodorizing tower are arranged in the order of steps between a carbon dioxide adsorption tower for obtaining compositional carbon dioxide from gas containing at least CO_2 and NO and a liquefaction purification device. A pre-processing device for raw material gas in a high-purity liquefied carbon dioxide production plant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63122892A JPH0780685B2 (en) | 1988-05-18 | 1988-05-18 | Method and apparatus for processing raw material gas in high-purity liquefied carbon dioxide production plant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63122892A JPH0780685B2 (en) | 1988-05-18 | 1988-05-18 | Method and apparatus for processing raw material gas in high-purity liquefied carbon dioxide production plant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01290517A true JPH01290517A (en) | 1989-11-22 |
| JPH0780685B2 JPH0780685B2 (en) | 1995-08-30 |
Family
ID=14847215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63122892A Expired - Lifetime JPH0780685B2 (en) | 1988-05-18 | 1988-05-18 | Method and apparatus for processing raw material gas in high-purity liquefied carbon dioxide production plant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780685B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202426A (en) * | 2009-02-27 | 2010-09-16 | Mitsubishi Heavy Ind Ltd | Apparatus and method for recovering co2 |
| JP2010533117A (en) * | 2007-07-13 | 2010-10-21 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method for purifying gas containing CO2 |
| WO2011068007A1 (en) * | 2009-12-02 | 2011-06-09 | 株式会社 東芝 | Device for separating and recovering carbon dioxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57205310A (en) * | 1981-06-08 | 1982-12-16 | Hoxan Corp | Producing apparatus for gaseous carbon dioxide |
| JPS5969415A (en) * | 1982-10-06 | 1984-04-19 | Ishikawajima Harima Heavy Ind Co Ltd | Manufacture of liquefied gaseous carbon dioxide |
| JPS61133117A (en) * | 1984-11-30 | 1986-06-20 | Ube Ind Ltd | Separation of gaseous carbon dioxide |
-
1988
- 1988-05-18 JP JP63122892A patent/JPH0780685B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57205310A (en) * | 1981-06-08 | 1982-12-16 | Hoxan Corp | Producing apparatus for gaseous carbon dioxide |
| JPS5969415A (en) * | 1982-10-06 | 1984-04-19 | Ishikawajima Harima Heavy Ind Co Ltd | Manufacture of liquefied gaseous carbon dioxide |
| JPS61133117A (en) * | 1984-11-30 | 1986-06-20 | Ube Ind Ltd | Separation of gaseous carbon dioxide |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010533117A (en) * | 2007-07-13 | 2010-10-21 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method for purifying gas containing CO2 |
| JP2010202426A (en) * | 2009-02-27 | 2010-09-16 | Mitsubishi Heavy Ind Ltd | Apparatus and method for recovering co2 |
| US8377184B2 (en) | 2009-02-27 | 2013-02-19 | Mitsubishi Heavy Industries, Ltd. | CO2 recovery apparatus and CO2 recovery method |
| WO2011068007A1 (en) * | 2009-12-02 | 2011-06-09 | 株式会社 東芝 | Device for separating and recovering carbon dioxide |
| CN102905773A (en) * | 2009-12-02 | 2013-01-30 | 株式会社东芝 | Device for separating and recovering carbon dioxide |
| AU2010327767B2 (en) * | 2009-12-02 | 2014-02-27 | Kabushiki Kaisha Toshiba | Device for separating and recovering carbon dioxide |
| AU2010327767C1 (en) * | 2009-12-02 | 2014-08-28 | Kabushiki Kaisha Toshiba | Device for separating and recovering carbon dioxide |
| US8926919B2 (en) | 2009-12-02 | 2015-01-06 | Kabushiki Kaisha Toshiba | Carbon dioxide separation and recovery apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0780685B2 (en) | 1995-08-30 |
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