JPH0351450B2 - - Google Patents
Info
- Publication number
- JPH0351450B2 JPH0351450B2 JP57232444A JP23244482A JPH0351450B2 JP H0351450 B2 JPH0351450 B2 JP H0351450B2 JP 57232444 A JP57232444 A JP 57232444A JP 23244482 A JP23244482 A JP 23244482A JP H0351450 B2 JPH0351450 B2 JP H0351450B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- oxidizing gas
- mixed
- oxidizing
- sintered body
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 claims description 32
- 230000001590 oxidative effect Effects 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910003439 heavy metal oxide Inorganic materials 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 description 64
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000005245 sintering Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000001272 pressureless sintering Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241001574715 Eremas Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 porphyrin metal complex Chemical class 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Carbon And Carbon Compounds (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Ceramic Products (AREA)
Description
本発明は、非酸化性ガス中に含有されるCOの
除去方法に係り、特に炭化物セラミツクス焼結体
の焼成時に雰囲気調整ガスとして用いられる非酸
化性ガス中に混入したCOをCO2化せしめた後除
去する非酸化性ガスの精製方法に関する。
炭化物セラミツクス焼結体は一般に化学的ある
いは物理的特性に優れたものが多く、なかでも炭
化珪素焼結体は硬度、熱伝導率、耐熱性、耐熱衝
撃性、化学的安定性などに極めて優れた特性を有
しており、ガスタービン部品、熱交換器のような
苛酷な条件下で使用される高温構造物の如き用途
に対して好適である。
前記炭化珪素焼結体の製造方法としては、反応
焼結法、加圧焼結法あるいは無加圧焼結法が広く
知られているが、なかでも無加圧焼結法は高密度
で複雑な形状をした焼結体を量産することのでき
る利点を有しており、その実用化が活発に進めら
れている。
ところで、炭化珪素焼結体の無加圧焼結法にお
いては焼結助剤として炭素質添加剤を使用するこ
とが必要であり、焼結時に炭化珪素粉末中に含有
される酸素と前期炭素質添加剤として添加された
炭素とが反応してCOが発生する。
前記焼結時の雰囲気中にCOが存在すると焼結
体の焼成収縮に大きな影響を及ぼし、焼結体を高
密度化することが困難になることが知られてお
り、特に高密度の焼結体を製造するに際しては焼
成時の雰囲気からCOを除去することが極めて重
要であり、通常前記COは非酸化性ガス気流によ
つて系外へ排出される。
しかしながら、前期炭化珪素の無加圧焼結時の
雰囲気ガスとして使用される非酸化性ガスは比較
的高価で使い捨てにすると不経済であるため、一
旦使用してCOが混入した非酸化性ガスはCOを除
去精製して繰返し使用することが好ましい。
ところで、COを含有する混合ガスよりCOを除
去あるいは分離する方法としては、例えば(1)ポル
フイリン金属錯体や活性炭などの吸着剤に吸着さ
せる方法、(2)塩化第１銅の塩酸溶液またはアンモ
ニア溶液などの吸収液に吸収させる方法、(3)接触
化触媒を使用してCOをCO2化せしめる方法等が
知られている。しかしながら、(1)の吸着剤に吸着
させる方法では吸着速度が比較的遅かつたり、
COの吸着と同時に離脱も生ずるため効率的にCO
を除去することが困難である。(2)の吸収液に吸収
させる方法では非酸化性ガス中に多量の水分が必
然的に混入する欠点を有する。(3)の接触酸化触媒
を使用してCOをCO2化せしめる方法としては燃
焼廃ガス中のCOを無害化する方法等が知られて
いるが、前期方法は燃焼廃ガス中に含有されてい
るかあるいは必要に応じて混合された酸化性ガス
によつてCOをCO2化せしめる方法であり、炭化
珪素の無加圧焼結時の雰囲気ガスとして使用され
た混合ガスは酸化性ガスを殆ど含有していないた
め前者の方法を適用することはできず、一方後者
の酸化性ガスを混入する方法は反応後に未反応の
酸化性ガスが残留することのないよいう酸化性ガ
スの混入量を適正に制御することが困難で実用的
でない。上述の如く、従来知られた方法はいずれ
も炭化珪素の無加圧焼結時に使用する非酸化性ガ
スの精製方法として適用することは困難であつ
た。
上述の如き観点から、本発明者らは非酸化性ガ
スを主体とし、COを含有する混合ガスよりCOを
効率的に除去する方法について種々検討した結
果、前期混合ガスを重金属酸化物と一定の条件下
で接触せしめることにより、前期混合ガス中に酸
化性ガスを全く混入させることなく、しかも極め
て効率的にCOをCO2化できることを知見し、本
発明を完成した。
本発明は非酸化性ガスを主体とし、COを含有
する混合ガスよりCOを安価にかつ容易に除去す
る方法を提供することを目的とするものである。
本発明によれば、非酸化性ガスを主体とし、
COを含有する混合ガスを重金属酸化物と接触せ
しめることにより、前期COを酸化せしめてCO2
となし、次いで前期CO2を吸収剤に吸収させて除
去することを特徴とする非酸化性ガスの精製方法
により、前記目的を達成することができる。
次に本発明を詳細に説明する。
本発明によれば、非酸化性ガスを主体とし、
COを含有する混合ガスを重金属酸化物と接触せ
しめることにより、前期COを酸化せしめてCO2
となすことが必要である。
前記重金属化物としては、例えはCu2O、CuO、
Fe2O3、Fe3O4、Mn2O3、Mn3O4、Pb3O4、PbO、
Co3O4、CoO、NiOあるいはそれらの複酸化物を
使用することができ、なかでも、Cu2O、Fe2O3、
Mn2O3、Pb3O4、Co3O4などがCOとの反応性に
優れ、効率的にCOをCO2化せしめることができ、
有利に使用できる。
前記重金属酸化物は、反応性が劣化した場合に
は酸化性雰囲気中で加熱して酸化せしめることに
より、繰返し使用することのできる利点を有す
る。
本発明によれば、重金属酸化物はCOとの接触
効率を高く維持することが有効であり、少なくと
も１m2／ｇの比表面積を有する粉末状あるいは多
孔質のものを使用することが有利である。
本発明において、前記COを酸化せしめてCO2
となす理由は、先にも述べた如くCOの状態では
吸着あるいは吸収によつて除去することが困難で
あるが、COを酸化せしめてCO2となすことによ
り、他に不純物を混入させることなく、吸収剤に
吸収させることができ、容易にかつ効率的に除去
することができるからである。
本発明によれは、前記混合ガスと前記重金属酸
化物とを200〜800℃の範囲内の温度で接触させる
ことが好ましい。その理由は、前記温度が200℃
より低いと混合ガスに含有されるCOをCO2化せ
しめる反応速度が遅く効率的でないからであり、
一方800℃より高いと一旦生成したCO2が分解し
て再びCOになつたり、前記重金属酸化物の焼結
反応が進行して比表面積が減少し、反応性が劣化
するばかりでなく、さらには再生して繰返し使用
することが困難になるからであり、300〜700℃の
範囲内で最も好適な結果を得ることができる。
本発明によれば、非酸化性ガスを主体とし、
COを含有する混合ガスは炭化物セラミツクス焼
結体を焼成する際に使用された雰囲気ガスであ
り、前記混合ガス中に含有されるCOガス含有量
は炭化物セラミツクス焼結体の焼結性を考慮する
と５％以下に維持することが有利である。前記混
合ガス中のCOガス含有量が５％より多くなると
焼結性が著しく劣化し、高密度の焼結体を得るこ
とが困難になる。
なお、本発明による非酸化性ガスの精製方法は
炭化珪素焼結体を製造する際に使用される雰囲気
調整ガスの精製方法として極めて好適に利用する
ことができる。
本発明によれば、前記非酸化性ガスとしては焼
結体および焼結設備に対して不活性なガスが使用
され、Ar、He、NeあるいはN2のなかから選ば
れるいずれか少なくとも１種を使用することが好
ましい。
本発明によれば、CO2の吸収剤としては水酸化
ナトリウム、水酸化カリウム、水酸化リチウム、
ソーダ石灰により選ばれるいずれか少なくとも１
種を使用することが好ましい。
なお、本発明によれば、COの除去率をさらに
向上させるために前述の如き非酸化性ガスの精製
操作を２回以上繰返し実施することもできる。
次に本発明を実施例について説明する。
実施例 １
第１図に示した如き装置を使用して、アルゴン
ガス中にCOガスを１％の割合で混入し、次いで
400℃に維持された酸化炉を５／minの割合で
15分間通過せしめ、ガス中のCOをCO2化した後、
吸収剤にCO2を選択的に吸収させ除去した。
酸化炉は内径30mmφの管状エレマ炉を使用し、
吸収管は内径20mmφのカルシウム管を使用した。
酸化炉には酸化第１銅粉末100ｇを酸化剤として
充てんし、吸収管には１〜５mmに整粒した水酸化
ナトリウム粒を100ｇ充てんした。
吸収管を通過させた後のアルゴンガス中に含有
されているCO濃度は約100ppmと極めて効率的に
COを精製除去することができた。
実施例２、比較例１
実施例１と同様であるが、第１表に示した如く
酸化剤および反応温度を変化させてアルゴンガス
中のCOガスを除去した。
結果は第１表に示した。
The present invention relates to a method for removing CO contained in a non-oxidizing gas, and in particular, a method for converting CO mixed in a non-oxidizing gas used as an atmosphere adjustment gas during firing of a carbide ceramic sintered body into CO2 . The present invention relates to a method for purifying non-oxidizing gas that is subsequently removed. Carbide ceramic sintered bodies generally have excellent chemical or physical properties, and silicon carbide sintered bodies are particularly excellent in hardness, thermal conductivity, heat resistance, thermal shock resistance, chemical stability, etc. These properties make it suitable for applications such as gas turbine parts, heat exchangers, and other high-temperature structures used under severe conditions. The reaction sintering method, pressure sintering method, and pressureless sintering method are widely known as methods for producing the silicon carbide sintered body, but among these, the pressureless sintering method has a high density and is complicated. It has the advantage of being able to mass-produce sintered bodies with various shapes, and its practical application is being actively promoted. By the way, in the pressureless sintering method of silicon carbide sintered bodies, it is necessary to use a carbonaceous additive as a sintering aid, and during sintering, the oxygen contained in the silicon carbide powder and the initial carbonaceous CO is generated by reaction with carbon added as an additive. It is known that the presence of CO in the atmosphere during sintering has a large effect on the sintering shrinkage of the sintered body, making it difficult to increase the density of the sintered body. When producing a body, it is extremely important to remove CO from the atmosphere during firing, and the CO is usually discharged out of the system by a non-oxidizing gas stream. However, the non-oxidizing gas used as the atmospheric gas during the pressureless sintering of silicon carbide is relatively expensive and uneconomical to dispose of once it is used. It is preferable to remove CO and purify it for repeated use. By the way, methods for removing or separating CO from a mixed gas containing CO include (1) adsorption to an adsorbent such as a porphyrin metal complex or activated carbon, and (2) a hydrochloric acid solution or an ammonia solution of cuprous chloride. (3) A method of converting CO into CO 2 using a contact catalyst is known. However, in method (1), the adsorption rate is relatively slow, and
Since CO adsorption and desorption occur at the same time, CO is efficiently absorbed.
is difficult to remove. The method (2) of absorbing into an absorbing liquid has the disadvantage that a large amount of water is inevitably mixed into the non-oxidizing gas. As for the method (3) of converting CO into CO 2 using a catalytic oxidation catalyst, there is a known method that detoxifies CO in the combustion waste gas, but the former method uses a catalytic oxidation catalyst to convert CO into CO 2 . This is a method in which CO is converted to CO 2 using an oxidizing gas mixed as necessary, and the mixed gas used as the atmospheric gas during pressureless sintering of silicon carbide contains almost no oxidizing gas. However, the latter method of mixing oxidizing gas requires adjusting the amount of oxidizing gas mixed so that no unreacted oxidizing gas remains after the reaction. difficult to control and impractical. As mentioned above, it has been difficult to apply any of the conventionally known methods as a method for purifying non-oxidizing gas used in pressureless sintering of silicon carbide. From the above-mentioned viewpoint, the present inventors investigated various methods for efficiently removing CO from a mixed gas containing CO, mainly consisting of non-oxidizing gas, and found that the mixed gas contains heavy metal oxides and a certain amount of CO. The present invention was completed based on the finding that CO can be converted into CO 2 very efficiently by contacting the gas under certain conditions without any oxidizing gas being mixed into the mixed gas. An object of the present invention is to provide a method for inexpensively and easily removing CO from a mixed gas containing CO, which is mainly composed of non-oxidizing gas. According to the present invention, the main component is a non-oxidizing gas,
By contacting a mixed gas containing CO with a heavy metal oxide, the previous CO is oxidized and converted into CO 2
The above object can be achieved by a method for purifying a non-oxidizing gas, which is characterized in that the CO 2 is removed by absorbing the CO 2 into an absorbent. Next, the present invention will be explained in detail. According to the present invention, the main component is a non-oxidizing gas,
By contacting a mixed gas containing CO with a heavy metal oxide, the previous CO is oxidized and converted into CO 2
It is necessary to do so. Examples of the heavy metal compound include Cu 2 O, CuO,
Fe 2 O 3 , Fe 3 O 4 , Mn 2 O 3 , Mn 3 O 4 , Pb 3 O 4 , PbO,
Co 3 O 4 , CoO, NiO or their double oxides can be used, among them Cu 2 O, Fe 2 O 3 ,
Mn 2 O 3 , Pb 3 O 4 , Co 3 O 4 , etc. have excellent reactivity with CO and can efficiently convert CO to CO 2 .
Can be used to advantage. The heavy metal oxide has the advantage that when its reactivity deteriorates, it can be used repeatedly by oxidizing it by heating in an oxidizing atmosphere. According to the present invention, it is effective to maintain high contact efficiency with CO, and it is advantageous to use a powdered or porous heavy metal oxide having a specific surface area of at least 1 m 2 /g. . In the present invention, the CO is oxidized to produce CO 2
The reason for this is that, as mentioned earlier, it is difficult to remove CO by adsorption or absorption in its state, but by oxidizing CO to CO 2 , it can be removed without contaminating other impurities. This is because it can be absorbed into an absorbent and removed easily and efficiently. According to the present invention, it is preferable that the mixed gas and the heavy metal oxide are brought into contact at a temperature within the range of 200 to 800°C. The reason is that the temperature is 200℃
This is because if it is lower, the reaction rate to convert CO contained in the mixed gas into CO2 will be slow and inefficient.
On the other hand, if the temperature is higher than 800°C, the CO 2 once generated will decompose and become CO again, and the sintering reaction of the heavy metal oxides will proceed, reducing the specific surface area, and not only will the reactivity deteriorate, but also This is because it becomes difficult to regenerate and use repeatedly, and the most suitable results can be obtained within the range of 300 to 700°C. According to the present invention, the main component is a non-oxidizing gas,
The mixed gas containing CO is the atmospheric gas used when firing the carbide ceramic sintered body, and the CO gas content contained in the mixed gas is determined by considering the sinterability of the carbide ceramic sintered body. It is advantageous to keep it below 5%. If the CO gas content in the mixed gas exceeds 5%, the sinterability will be significantly degraded, making it difficult to obtain a high-density sintered body. Note that the method for purifying non-oxidizing gas according to the present invention can be very suitably used as a method for purifying atmosphere adjustment gas used when manufacturing a silicon carbide sintered body. According to the present invention, as the non-oxidizing gas, a gas inert to the sintered body and sintering equipment is used, and at least one selected from Ar, He, Ne, or N2 is used. It is preferable to use According to the present invention, the CO 2 absorbent includes sodium hydroxide, potassium hydroxide, lithium hydroxide,
At least one selected from soda lime
Preferably, seeds are used. According to the present invention, the above-described non-oxidizing gas purification operation can be repeated two or more times in order to further improve the CO removal rate. Next, the present invention will be explained with reference to examples. Example 1 Using the apparatus shown in Figure 1, CO gas was mixed into argon gas at a ratio of 1%, and then
Oxidation furnace maintained at 400℃ at a rate of 5/min
After passing through the gas for 15 minutes and converting the CO in the gas to CO2 ,
CO 2 was selectively absorbed and removed by the absorbent. The oxidation furnace uses a tubular EREMA furnace with an inner diameter of 30 mmφ.
The absorption tube used was a calcium tube with an inner diameter of 20 mmφ.
The oxidation furnace was filled with 100 g of cuprous oxide powder as an oxidizing agent, and the absorption tube was filled with 100 g of sodium hydroxide grains sized to 1 to 5 mm. The CO concentration in the argon gas after passing through the absorption tube is approximately 100 ppm, which is extremely efficient.
CO could be purified and removed. Example 2, Comparative Example 1 Same as Example 1, but CO gas in argon gas was removed by changing the oxidizing agent and reaction temperature as shown in Table 1. The results are shown in Table 1.
【表】
実施例 ３
第２図に示した如き非酸化性ガス精製装置を使
用して炭化珪素無加圧焼結体を焼成する際に使用
した雰囲気調整排ガス中のCOを除去精製した。
酸化炉は内径が60mmφの堅型管状エレマ炉を使
用し、500℃に保持された均熱帯には酸化剤とし
てMn3O4を主成分とする酸化マンガン粉末200ｇ
を装入し、吸収管には0.3〜0.6mmの粒径範囲に整
粒した水酸化ナトリウムを200ｇ装入した。
焼結炉より排出される雰囲気調整ガス中に含有
されるCOの含有率は焼成温度が約1550℃に到達
した時点で最大となり、3.7％であることが確認
された。なお、雰囲気調整ガスはアルゴンガスを
使用し、28／minの割合で焼成炉中へ装入し
た。
精製後のアルゴンガス中に含有されるCOの含
有率は常に200ppm以下であり、極めて効率よく
COを除去することができ、再利用することがで
きた。
なお、本実施例で焼成された炭化珪素無加圧焼
結体ほ収縮性も良好で極めて緻密質であつた。
以上述べた如く、本発明によれば、炭化物セラ
ミツクス焼結体の焼成時に雰囲気調整ガスとして
用いられる非酸化性ガス中に混入したCOを容易
にかつ安価に除去精製し、再利用することを可能
にするものであつて、産業に寄与する効果は極め
て大きい。[Table] Example 3 A non-oxidizing gas purification apparatus as shown in FIG. 2 was used to remove and purify CO in the atmosphere-adjusted exhaust gas used when firing a pressureless sintered silicon carbide body. The oxidation furnace is a rigid tubular EREMA furnace with an inner diameter of 60mmφ, and in the soaking zone maintained at 500℃, 200g of manganese oxide powder whose main component is Mn 3 O 4 is used as an oxidizing agent.
200g of sodium hydroxide sized to a particle size range of 0.3 to 0.6mm was charged to the absorption tube. It was confirmed that the content of CO contained in the atmosphere adjustment gas discharged from the sintering furnace reached its maximum at 3.7% when the sintering temperature reached approximately 1550°C. Note that argon gas was used as the atmosphere adjustment gas, and was charged into the firing furnace at a rate of 28/min. The content of CO contained in argon gas after purification is always less than 200 ppm, making it extremely efficient.
CO could be removed and reused. Note that the silicon carbide pressureless sintered body fired in this example had good shrinkability and was extremely dense. As described above, according to the present invention, it is possible to easily and inexpensively remove and purify CO mixed in the non-oxidizing gas used as an atmosphere adjustment gas when firing a carbide ceramic sintered body, and reuse it. The effect of contributing to industry is extremely large.
第１図は、本発明の実施例１において使用した
実験装置の模式図、第２図は、本発明の実施例に
おいて使用した非酸化性ガス精製装置の模式図で
ある。
１……アルゴンガスボンベ、２……COガスボ
ンベ、３……流量計、４……ガス混合機、５……
配管、６……管状エレマ炉、７……酸化剤、８…
…吸収管、９……吸収剤、１０……焼成炉、１１
……ブロアー、１２……バルブ、１３……パージ
用バルブ。
FIG. 1 is a schematic diagram of the experimental apparatus used in Example 1 of the present invention, and FIG. 2 is a schematic diagram of the non-oxidizing gas purification apparatus used in the Example of the present invention. 1... Argon gas cylinder, 2... CO gas cylinder, 3... Flow meter, 4... Gas mixer, 5...
Piping, 6...Tubular EREMA furnace, 7...Oxidizing agent, 8...
...Absorption tube, 9...Absorbent, 10...Calcination furnace, 11
...Blower, 12...Valve, 13...Purge valve.
Claims (1)
合ガスを重金属酸化物と接触せしめることによ
り、前記混合ガス中に酸化性ガスを混入させるこ
となく前記COを酸化せしめてCO2となし、次い
で前記CO2を吸収剤に吸収させて除去することを
特徴とする非酸化性ガスの精製方法。 ２ 前記重金属酸化物は、Cu、Fe、Pb、Mn、
Co、Niより選ばれるいずれか少なくとも１種の
酸化物である特許請求の範囲第１項記載の方法。 ３ 前記混合ガスは、炭化物セラミツクス焼結体
を焼成する際に雰囲気調整ガスとして使用された
ものである特許請求の範囲第１あるいは２項記載
の方法。 ４ 前記炭化物セラミツクス焼結体は、炭化珪素
焼結体である特許請求の範囲第３項記載の方法。 ５ 前記非酸化性ガスは、Ar、He、Neあるい
はN2のなかから選ばれるいずれか少なくとも１
種である特許請求の範囲第１〜４項のいずれかに
記載の方法。 ６ 前記混合ガスと前記重金属酸化物とを200〜
800℃の温度範囲内で接触させる特許請求の範囲
第１〜５項のいずれかに記載の方法。 ７ 前記吸収剤は水酸化ナトリウム、水酸化カリ
ウム、水酸化リチウム、ソーダ石灰より選ばれる
いずれか少なくとも１種である特許請求の範囲第
１〜６項のいずれかに記載の方法。[Scope of Claims] 1. A mixed gas mainly consisting of non-oxidizing gas and containing CO is brought into contact with a heavy metal oxide to oxidize the CO without mixing oxidizing gas into the mixed gas. 1. A method for purifying non-oxidizing gas, which comprises converting CO 2 into CO 2 and then removing the CO 2 by absorbing the CO 2 into an absorbent. 2 The heavy metal oxides include Cu, Fe, Pb, Mn,
The method according to claim 1, wherein the oxide is at least one selected from Co and Ni. 3. The method according to claim 1 or 2, wherein the mixed gas is used as an atmosphere adjusting gas when firing a carbide ceramic sintered body. 4. The method according to claim 3, wherein the carbide ceramic sintered body is a silicon carbide sintered body. 5 The non-oxidizing gas is at least one selected from Ar, He, Ne, or N2 .
The method according to any one of claims 1 to 4, which is a species. 6 The mixed gas and the heavy metal oxide are mixed at a temperature of 200~
6. A method according to any one of claims 1 to 5, wherein the contact is carried out within a temperature range of 800<0>C. 7. The method according to any one of claims 1 to 6, wherein the absorbent is at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, and soda lime.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57232444A JPS59120222A (en) | 1982-12-27 | 1982-12-27 | Purification of non-oxidative gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57232444A JPS59120222A (en) | 1982-12-27 | 1982-12-27 | Purification of non-oxidative gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59120222A JPS59120222A (en) | 1984-07-11 |
| JPH0351450B2 true JPH0351450B2 (en) | 1991-08-06 |
Family
ID=16939364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57232444A Granted JPS59120222A (en) | 1982-12-27 | 1982-12-27 | Purification of non-oxidative gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59120222A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61127613A (en) * | 1984-11-22 | 1986-06-14 | Mitsui Toatsu Chem Inc | Purifying method of carbon dioxide |
| US4623524A (en) * | 1985-02-08 | 1986-11-18 | Hitachi, Ltd. | Process and apparatus for recovering inert gas |
| JPS61236603A (en) * | 1985-04-10 | 1986-10-21 | Nippon Cement Co Ltd | Continuous synthesizing device for nonoxide powder |
| JPH0624962B2 (en) * | 1985-11-15 | 1994-04-06 | 日本酸素株式会社 | Method for recovering high-purity argon from exhaust gas from a single crystal manufacturing furnace |
| KR20020096026A (en) * | 2002-10-16 | 2002-12-28 | 장성진 | Method and apparatus for producing basic or inert gases of a high degree of purity |
| JP5202836B2 (en) * | 2006-12-01 | 2013-06-05 | 日本エア・リキード株式会社 | Xenon recovery system and recovery device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147568A (en) * | 1974-10-22 | 1976-04-23 | Sunao Yamagata |
-
1982
- 1982-12-27 JP JP57232444A patent/JPS59120222A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147568A (en) * | 1974-10-22 | 1976-04-23 | Sunao Yamagata |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59120222A (en) | 1984-07-11 |
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