JP2756736B2 - Method for purifying hydrogen-containing CO gas - Google Patents
Method for purifying hydrogen-containing CO gasInfo
- Publication number
- JP2756736B2 JP2756736B2 JP3175817A JP17581791A JP2756736B2 JP 2756736 B2 JP2756736 B2 JP 2756736B2 JP 3175817 A JP3175817 A JP 3175817A JP 17581791 A JP17581791 A JP 17581791A JP 2756736 B2 JP2756736 B2 JP 2756736B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- gas
- catalyst
- acetic acid
- reaction
- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Industrial Gases (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、水素含有COガスの精
製方法および該方法により得られる精製COガスを用い
る酢酸製造方法に関する。The present invention relates to a method for purifying hydrogen-containing CO gas and a method for producing acetic acid using purified CO gas obtained by the method.
【0002】[0002]
【従来の技術およびその課題】従来、酢酸製造原料など
としての水素含有COガスとしては、石炭、石油、天然
ガスなどを用いて部分燃焼反応、水蒸気改質反応などに
より得られる、いわゆる合成ガスを用いることが知られ
ており、この合成ガスには、通常20〜60容量%の水
素が含まれている。2. Description of the Related Art Conventionally, as a hydrogen-containing CO gas as a raw material for producing acetic acid, a so-called synthesis gas obtained by a partial combustion reaction, a steam reforming reaction or the like using coal, petroleum, natural gas, or the like has been used. It is known to be used, this synthesis gas usually containing 20 to 60% by volume of hydrogen.
【0003】上記水素含有COガスの精製方法として
は、従来、膜分離法、銅アンモニア法、COSORB
法、深冷分離法、活性アルミナに炭素を添着し、これに
CuClおよびCuCl2 を担持させた吸着剤のCO選
択吸着力を利用した吸着法、すなわちPSA(圧力スイ
ング吸着法)など水素含有COガス中の水素除去方法が
知られているが、何れの方法も微量の水素まで除去する
のは困難であった。Conventional methods for purifying the hydrogen-containing CO gas include a membrane separation method, a copper ammonia method, and COSORB.
Method, cryogenic separation method, adsorption method utilizing carbon selective adsorption of adsorbent obtained by impregnating activated alumina with carbon and supporting CuCl and CuCl 2 , that is, hydrogen-containing CO such as PSA (pressure swing adsorption method) Methods for removing hydrogen from gas are known, but it has been difficult to remove even trace amounts of hydrogen by any of the methods.
【0004】例えば、特公昭60−43767号公報に
は、炭素質担体に、ニッケル、コバルトあるいはそれら
の化合物を担持してなるアルコールのカルボニル化触
媒、さらには該触媒とヨウ素化合物助触媒の存在下、メ
タノールと一酸化炭素とを気相接触反応させて酢酸を製
造する方法が開示されているが、水素含有COガス、い
わゆる合成ガスを原料として用いることについては、具
体的な記載も、その効果を確認するに足る記載もなく、
得られる酢酸の選択率および収率も低く満足すべき状態
ではない。For example, Japanese Patent Publication No. 60-43767 discloses a catalyst for carbonylation of alcohol comprising nickel or cobalt or a compound thereof supported on a carbonaceous carrier, and further comprising a catalyst comprising the catalyst and an iodine compound cocatalyst. A method for producing acetic acid by reacting methanol and carbon monoxide in a gas phase is disclosed. However, the use of a hydrogen-containing CO gas, a so-called synthesis gas, as a raw material is not specifically described, but its effects are also described. There is no description enough to confirm
The selectivity and yield of the acetic acid obtained are also low and not satisfactory.
【0005】ケミストリー・レターズ(Chemistry Lett
ers)、895〜898頁、1987年には、活性炭担
持ニッケル触媒の存在下のメタノールの気相カルボニル
化反応における水素の反応促進効果について、酢酸の収
率は、H2 /CO比が0.1以上のとき最高値に達する
旨報告されており、水素を含有しない一酸化炭素を使用
した場合に比べて一酸化炭素と水素を、H2 /CO比が
0.1以上の量だけ存在させることにより酢酸の収率は
向上しているが、まだ満足すべき状態ではない。[0005] Chemistry Letters
ers), pp. 895-898, 1987, on the effect of accelerating hydrogen in the gas-phase carbonylation reaction of methanol in the presence of a nickel catalyst supported on activated carbon, the yield of acetic acid with an H 2 / CO ratio of 0. It is reported that the maximum value is reached when the ratio is 1 or more, and carbon monoxide and hydrogen are present in an amount of H 2 / CO ratio of 0.1 or more as compared with the case where carbon monoxide containing no hydrogen is used. As a result, the yield of acetic acid has been improved, but is not yet satisfactory.
【0006】プロシーディング・オブ・ナインス・イン
ターナショナル・キャタリシス・コングレス(Proceedi
ng of 9th International Catalysis Congress)、vol.
3、p1051〜1058(1988)には、活性炭担体ロジウム金
属触媒について、メタノールのカルボニル化反応による
酢酸の生成における活性がすぐれていること、および例
えば523°K、11気圧、W/F=5g・h/モル
(Rh:1g・h/モル)およびCO/MeOH/Me
I/H2 =50/9/1/(19)(モル)の条件下で
水素を共存させることにより、酢酸生成反応の活性が水
素を共存させない場合に比べて向上する旨教示されてい
るに過ぎず、該触媒および水素共存の影響についての詳
細は明らかにされていない。[0006] Proceedi of Ninth International Catalysis Congress
ng of 9th International Catalysis Congress), vol.
3, p 1051-1058 (1988), that the activated carbon-supported rhodium metal catalyst has excellent activity in the production of acetic acid by the carbonylation reaction of methanol and, for example, 523 ° K, 11 atm, W / F = 5 g · h / mol (Rh: 1 g · h / mol) and CO / MeOH / Me
It is taught that the coexistence of hydrogen under the condition of I / H 2 = 50/9/1 / (19) (mol) improves the activity of the acetic acid formation reaction as compared with the case without coexisting hydrogen. The details of the effect of the coexistence of the catalyst and hydrogen are not disclosed.
【0007】特公昭47−3334号公報には、ロジウ
ム錯体触媒を用い、ヨウ化メチルあるいはヨウ化水素を
促進剤としてメタノールを液相でカルボニル化して高収
率で酢酸を製造する方法が開示されているが、反応系が
著しく腐食性で高価な耐蝕材料を必要とすること、生成
物と触媒の分離に特別な工程を必要とすること、メタン
の副生が多いこと、などの欠点があり、水素含有COガ
ス、いわゆる合成ガスを原料として用いることについて
は、具体的な記載も、その効果を確認するに足る記載も
ない。Japanese Patent Publication No. 47-3334 discloses a method for producing acetic acid in high yield by carbonylation of methanol in a liquid phase using a rhodium complex catalyst and methyl iodide or hydrogen iodide as an accelerator. However, it has disadvantages such as the fact that the reaction system is extremely corrosive and requires expensive corrosion-resistant materials, a special process is required for separating the product and the catalyst, and there are many by-products of methane. The use of hydrogen-containing CO gas, a so-called synthesis gas, as a raw material has neither a specific description nor a description sufficient to confirm its effect.
【0008】従来、例えばアンモニア合成などにおい
て、COガスと水素ガスとの混合ガスであって、水素ガ
ス含有量が99容量%以上と高い場合には、ニッケル触
媒などの存在下、比較的低温でメタン化反応が進行する
ことが知られている。Conventionally, for example, in the synthesis of ammonia or the like, when a mixed gas of CO gas and hydrogen gas and the hydrogen gas content is as high as 99% by volume or more, at a relatively low temperature in the presence of a nickel catalyst or the like. It is known that the methanation reaction proceeds.
【0009】しかしながら、CO含有量が高く、水素含
有量が低い場合に、ニッケル触媒などの従来公知の触媒
を用いると、COの分解により炭素が析出し、COの収
率が低下すると共に触媒の劣化、反応器の閉塞を起こし
たり、ニッケル触媒ではニッケルカルボニルの生成によ
り昇華が起きたり、COが触媒表面に強く吸着して反応
を阻害したりする欠点があった。However, when a conventionally known catalyst such as a nickel catalyst is used when the content of CO is high and the content of hydrogen is low, carbon is precipitated due to decomposition of CO, the yield of CO decreases, and the Deterioration and clogging of the reactor occur, nickel catalysts cause sublimation due to formation of nickel carbonyl, and CO is strongly adsorbed on the catalyst surface to hinder the reaction.
【0010】本発明は、炭素の析出がなく、カルボニル
化合物の生成による昇華もなく、比較的少量の水素を含
有するCOガス中の水素を極微量にまで除去しうる水素
含有COガスの精製方法、ならびに該方法により得られ
る精製COガスを用い、簡略化された製造工程で、反応
系の腐食性が著しく低減され、しかも高選択率および高
収率で酢酸を製造する方法を提供することを目的とする
ものである。The present invention provides a method for purifying a hydrogen-containing CO gas which does not precipitate carbon, does not cause sublimation due to the formation of a carbonyl compound, and can remove a very small amount of hydrogen in a CO gas containing a relatively small amount of hydrogen. And a method for producing acetic acid with high selectivity and high yield in which the corrosiveness of the reaction system is significantly reduced in a simplified production process using purified CO gas obtained by the method. It is the purpose.
【0011】本発明は、白金、パラジウムおよびロジウ
ムよりなる群から選ばれた白金族系金属を耐熱性担体に
担持してなる触媒を充填した反応器に、水素含有COガ
スを導入させ、一定条件下で接触的にメタン化反応を行
わせて該ガス中に含まれる水素を除去することを特徴と
する水素含有COガスの精製方法を提供するものであ
る。該方法により得られる精製COガスは、水素含有量
が2容量%以下である該精製COガスを、炭素質担体ロ
ジウム金属触媒およびヨウ化メチル促進剤の存在下に、
気相状態でメタノールと接触反応させることを特徴とす
る酢酸製造方法に用いられる。 The present invention relates to platinum, palladium and rhodium.
A hydrogen-containing CO gas is introduced into a reactor filled with a catalyst in which a platinum group metal selected from the group consisting of A method for purifying hydrogen-containing CO gas, which comprises removing hydrogen contained in the gas by the method.
You . The purified CO gas obtained by the method is obtained by converting the purified CO gas having a hydrogen content of 2% by volume or less to a carbonaceous carrier rhodium metal catalyst and a methyl iodide promoter.
It is used in a method for producing acetic acid, which comprises reacting with methanol in a gas phase .
【0012】本発明の水素含有COガス精製方法に用い
られる水素含有COガスとしては、例えば石炭、石油、
天然ガスを用いて部分燃焼、水蒸気改質反応などにより
得られる、いわゆる合成ガスであって、その水素含有量
が20〜75容量%のものや、CO2 を水素還元して得
られ、その水素含有量が5〜75容量%のものなどがあ
げられる。この高濃度水素はあらかじめ膜分離法、銅ア
ンモニア法、COSORB法、PSA法などの水素除去
方法である程度まで除去してもよい。The hydrogen-containing CO gas used in the hydrogen-containing CO gas purification method of the present invention includes, for example, coal, petroleum,
A so-called synthesis gas obtained by partial combustion, steam reforming reaction, or the like using natural gas, having a hydrogen content of 20 to 75% by volume, or obtained by reducing CO 2 with hydrogen, Those having a content of 5 to 75% by volume are exemplified. The high-concentration hydrogen may be removed to some extent in advance by a hydrogen removal method such as a membrane separation method, a copper ammonia method, a COSORB method, or a PSA method.
【0013】本発明における水素含有COガスの精製方
法は、白金族系金属、好ましくは白金を耐熱性担体、好
ましくはガンマー・アルミナ担体に担持してなる触媒を
充填した反応器に、上記水素含有COガスを導入させて
接触的にメタン化反応を行なわせて水素含有COガス中
の水素を除去する方法である。[0013] The method for purifying hydrogen-containing CO gas in the present invention is a method of purifying a hydrogen-containing CO gas in a reactor filled with a catalyst comprising a platinum group metal, preferably platinum, supported on a heat-resistant carrier, preferably a gamma-alumina carrier. This is a method in which CO gas is introduced and a methanation reaction is performed catalytically to remove hydrogen in the hydrogen-containing CO gas.
【0014】本発明の水素含有COガス精製方法におい
て用いられる触媒は、公知の触媒製法を適宜選択すれば
良いが、通常、含浸法、沈着法、浸漬法、イオン交換
法、蒸着法、混練法により白金族系金属を耐熱性担体に
担持させたのち、50〜200℃、好ましくは80〜1
20℃で水分を蒸発させる乾燥操作を行ない、200〜
800℃、好ましくは300〜600℃で焼成を行なっ
たのち、更に100〜700℃、好ましくは200〜5
00℃で水素含有ガスを流通させて触媒の還元を行なう
水素還元処理を施す方法により製造される。還元はヒド
ラジンやホルマリンとアルカリによる溶液還元もでき
る。溶液還元の場合は乾燥操作ののち、焼成を行なわず
に溶液還元に移れば良い。なお、含浸法などで使用する
白金族系金属試薬としては、塩化物、硝酸塩、水酸化
物、テトラクロロ白金酸(II) (IV)、白金黒などが使用
できる。白金の場合はテトラクロロ白金酸(IV)が好ま
しい。また、触媒還元はCOガス精製時に行なわれるた
め、還元処理は必ずしも必要でない。The catalyst used in the hydrogen-containing CO gas refining method of the present invention may be appropriately selected from known catalyst production methods, and usually includes an impregnation method, a deposition method, an immersion method, an ion exchange method, a vapor deposition method, and a kneading method. After the platinum group metal is supported on the heat-resistant carrier, the temperature is 50 to 200 ° C., preferably 80 to 1 ° C.
A drying operation for evaporating water at 20 ° C. is performed,
After firing at 800 ° C., preferably 300 to 600 ° C., the firing is further performed at 100 to 700 ° C., preferably 200 to 5 ° C.
It is manufactured by a method of performing a hydrogen reduction treatment of reducing a catalyst by flowing a hydrogen-containing gas at 00 ° C. For the reduction, solution reduction with hydrazine, formalin and alkali can also be performed. In the case of the solution reduction, after the drying operation, the process may be shifted to the solution reduction without performing the firing. In addition, as the platinum group metal reagent used in the impregnation method or the like, chloride, nitrate, hydroxide, tetrachloroplatinic acid (II) (IV), platinum black and the like can be used. In the case of platinum, tetrachloroplatinic acid (IV) is preferred. Further, since the catalyst reduction is performed during the purification of the CO gas, the reduction treatment is not necessarily required.
【0015】本発明の水素含有COガス精製方法におい
て用いられる白金族金属としては、白金、ハラジウムお
よびロジウムがあげられるが、白金が特に好ましい。The platinum group metals used in the method for purifying hydrogen-containing CO gas of the present invention include platinum, haradium and the like .
And rhodium , with platinum being particularly preferred.
【0016】本発明の水素含有COガス精製方法におい
て用いられる耐熱性担体としては、ガンマー・アルミ
ナ、アルファー・アルミナ、活性炭、ゼオライト、シリ
カ、シリカ・アルミナ、チタニア、ジルコニア、マグネ
シアなどがあげられるが、ガンマー・アルミナが特に好
ましい。The heat-resistant carrier used in the method for purifying hydrogen-containing CO gas of the present invention includes gamma-alumina, alpha-alumina, activated carbon, zeolite, silica, silica-alumina, titania, zirconia, and magnesia. Gamma alumina is particularly preferred.
【0017】本発明の水素含有COガス精製方法におけ
るメタン化反応は、例えば反応温度150〜550℃、
好ましくは200〜500℃、反応圧力0〜200kg
/cm2 ・G、好ましくは0〜100kg/cm2 ・
G、W/F0.1〜100g・h/モル、好ましくは1
〜30g・h/モルの条件下に行なわれる。ただし、反
応圧力には特に制限はなく、高い方が好ましいが、減圧
でもよい。The methanation reaction in the method for purifying hydrogen-containing CO gas of the present invention is carried out, for example, at a reaction temperature of 150 to 550 ° C.
Preferably 200-500 ° C, reaction pressure 0-200kg
/ Cm 2 · G, 2 · preferably 0~100kg / cm
G, W / F 0.1 to 100 g · h / mol, preferably 1
The reaction is performed under the conditions of 30 g · h / mol. However, the reaction pressure is not particularly limited and is preferably higher, but may be reduced.
【0018】本発明の水素含有COガスの精製方法にお
いて、該方法により得られる精製COガスを酢酸製造の
原料として用いることができるが、その場合、水素含有
量を2容量%以下、好ましくは1容量%以下まで精製す
る必要がある。In the method for purifying hydrogen-containing CO gas of the present invention, the purified CO gas obtained by the method can be used as a raw material for producing acetic acid. In this case, the hydrogen content is 2% by volume or less, preferably 1% by volume or less. It is necessary to purify to below volume%.
【0019】前記酢酸製造方法における炭素質担体ロジ
ウム金属触媒に用いられる炭素質担体の例として、活性
炭、カーボンブラック、コークスなどのほかに炭素質を
担持したシリカ、アルミナ、ゼオライトなどの無機質担
体があげられるが、これらのうち活性炭が好ましい。[0019] Examples of the carbonaceous carrier used carbonaceous support rhodium metal catalyst in the production of acetic acid method, activated carbon, carbon black, silica and other carrying carbonaceous in such coke, alumina, inorganic carriers such as zeolites mentioned Of these, activated carbon is preferred.
【0020】前記酢酸製造方法において用いられる炭素
質担体ロジウム金属触媒は、通常含浸法、沈着法、浸漬
用、蒸着法、混練法などによりRhを炭素質担体に担持
させたのち、50〜200℃、好ましくは80〜120
℃で水分を蒸発させる乾燥操作を行ない、更に100〜
700℃、好ましくは200〜400℃で水素含有ガス
を流通させて触媒の還元を行なう水素還元処理を施こす
方法により製造される。還元はホルマリンとアルカリに
よる溶液還元もできる。なお、含浸法などで使用するR
h試薬としては、塩化ロジウム、塩化ロジウム酸ナトリ
ウム、塩化ロジウム酸アンモニウム、水酸化ロジウムな
どが使用できる。特に塩化ロジウムが好ましい。また、
触媒還元は酢酸製造時に行われるため、還元処理はかな
らずしも必要でない。The carbonaceous support rhodium metal catalyst used in the acetic acid production process, typically impregnation method, after deposition method, a dip, a vapor deposition method, the Rh due kneading method was supported on a carbonaceous carrier, 50 to 200 ° C. , Preferably 80 to 120
Perform a drying operation to evaporate water at a temperature of 100 ° C.
It is manufactured by a method in which a hydrogen-containing gas is passed at 700 ° C., preferably 200 to 400 ° C. to perform a hydrogen reduction treatment for reducing the catalyst. For the reduction, solution reduction with formalin and alkali can also be performed. In addition, R used in the impregnation method
As the reagent h, rhodium chloride, sodium rhodate, ammonium rhodate, rhodium hydroxide and the like can be used. Particularly, rhodium chloride is preferred. Also,
Since the catalytic reduction is performed during the production of acetic acid, a reduction treatment is not always necessary.
【0021】前記酢酸製造方法におけるヨウ化メチル促
進剤の使用量は、特に制限されるものではないが、通常
メタノール100モルに対して0.1〜50モル、好ま
しくは1〜20モルの範囲である。該促進剤として、ヨ
ウ化メチルの代りにメタノールとの反応により装置内で
ヨウ化メチルを生成するヨウ素化合物、例えばヨウ素、
ヨウ化水素などを用いることもできる。[0021] The amount of methyl iodide promoter in the acetic acid production process, is not particularly limited, 0.1 to 50 mol relative to normal methanol 100 moles, preferably 1 to 20 mols is there. As the promoter, an iodine compound which produces methyl iodide in a device by reacting with methanol instead of methyl iodide, for example, iodine;
Hydrogen iodide and the like can also be used.
【0022】前記酢酸製造方法における触媒反応は、上
記炭素質担体ロジウム金属触媒および上記ヨウ化メチル
促進剤の存在下、メタノールと水素含有量2容量%、好
ましくは1容量%以下のCOガスとを、メタノールとC
Oガスとの使用割合、CO:メタノールモル比=1:1
00〜100:1、好ましくは1:10〜10:1、反
応温度100〜400℃、好ましくは150〜300
℃、反応圧力0.1〜300気圧、好ましくは1〜10
0気圧、W/F0.1〜500g・h/モル、好ましく
は1〜30g・h/モルの条件下、気相状態で反応させ
ることにより行なわれる。The catalytic reaction in the production of acetic acid method, the presence of the carbonaceous support rhodium metal catalyst and the methyl iodide promoter, methanol and hydrogen content 2% by volume, preferably a 1% by volume or less of CO gas , Methanol and C
Use ratio with O gas, CO: methanol molar ratio = 1: 1
00 to 100: 1, preferably 1:10 to 10: 1, reaction temperature 100 to 400 ° C, preferably 150 to 300
° C, reaction pressure 0.1-300 atm, preferably 1-10
The reaction is carried out in a gas phase under the conditions of 0 atm and W / F of 0.1 to 500 g · h / mol, preferably 1 to 30 g · h / mol.
【0023】上記水素含有COガス中に不純物として水
およびメタンが存在しても触媒作用を妨害することはな
い。上記反応温度が400℃を超えるとメタンの生成量
が増大するので好ましくない。本発明方法における接触
反応に用いられる反応器としては、特に制限されるもの
ではなく、固定床、流動床および移動床のいずれでもよ
い。The presence of water and methane as impurities in the hydrogen-containing CO gas does not hinder the catalytic action. If the reaction temperature exceeds 400 ° C., the amount of methane produced is undesirably increased. The reactor used for the catalytic reaction in the method of the present invention is not particularly limited, and may be any of a fixed bed, a fluidized bed and a moving bed.
【0024】メタノールとCOガスとの反応は、基本的
にはいったん酢酸メチルと水を生成し、さらに酢酸メチ
ルと水が反応して酢酸とメタノールになり、生成したメ
タノールは原料として利用される。しかし、上記した反
応条件下、水素が共存すると酢酸メチルと水素が反応し
て酢酸と同時にメタンを生成し、酢酸の収率が低下する
ことになる。一方、水素が共存すると、促進剤のヨウ化
メチルと水素が反応し、ヨウ化メチルの分解が起きて、
酢酸生成反応を阻害すると共に、ヨウ化メチル分解生成
物であるヨウ素およびヨウ化水素は腐食性であり、製造
装置の腐食の原因ともなる。The reaction between methanol and CO gas basically generates methyl acetate and water once, and further reacts the methyl acetate with water to form acetic acid and methanol, and the generated methanol is used as a raw material. However, when hydrogen coexists under the above reaction conditions, methyl acetate and hydrogen react with each other to produce methane at the same time as acetic acid, thereby lowering the yield of acetic acid. On the other hand, when hydrogen coexists, methyl iodide as a promoter reacts with hydrogen to cause decomposition of methyl iodide,
In addition to inhibiting the acetic acid production reaction, iodine and hydrogen iodide, which are methyl iodide decomposition products, are corrosive and cause corrosion of production equipment.
【0025】前記酢酸製造方法の1例のフローチャート
図は、図2の通りである。The flow chart of an example of the acetic acid production process is as FIG.
【0026】[0026]
【図2】FIG. 2
【0027】[0027]
【発明の効果】本発明の水素含有COガス精製方法によ
れば、炭素の析出がなく、カルボニル化合物の生成によ
る昇華もなく、比較的少量の水素を含有するCOガス中
の水素を極微量にまで除去することが可能であり、特に
酢酸製造用原料として好適な精製COガスが得られる効
果がある。なお、本発明方法で得られる精製COガス
は、例えばPhNO2のカルボニル化反応によりPhN
HCO2Rを製造する場合など、水素の共存が望ましく
ない場合にも用いることができる。前記酢酸製造方法に
よれば、上記精製COガスを用いることと相俟って、
(1)促進剤としてのヨウ化メチルの消耗が減少し、酢
酸生成反応が阻害されることがなく、かつヨウ素および
ヨウ化水素の副生がなく、製造装置の腐食が防止される
こと、(2)メタンの副生量が減少し、そのため生成物
から未反応のCOガスを回収する際に回収ガスにメタン
が少量しか含まれず、メタン分離操作なしに原料として
再利用できること、および(3)上記利点と共に高選択
率および高収率で酢酸を製造することができることの効
果が得られる。According to the method for purifying hydrogen-containing CO gas of the present invention, there is no precipitation of carbon, no sublimation due to the formation of carbonyl compounds, and a very small amount of hydrogen in CO gas containing a relatively small amount of hydrogen. It is possible to obtain purified CO gas suitable as a raw material for producing acetic acid. Incidentally, the purified CO gas obtained in the method of the present invention, for example, by the carbonylation reaction of PhNO 2 PhN
It can also be used when coexistence of hydrogen is not desirable, such as in the case of producing HCO 2 R. According to the acetic acid production process, coupled with the use of the above purification CO gas,
(1) The consumption of methyl iodide as a promoter is reduced, the acetic acid production reaction is not hindered, and there is no by-product of iodine and hydrogen iodide, and corrosion of the production equipment is prevented. 2) the amount of by-products of methane is reduced, so that when recovering unreacted CO gas from the product, the recovered gas contains only a small amount of methane and can be reused as a raw material without a methane separation operation; and (3) The effect of being able to produce acetic acid with high selectivity and high yield is obtained together with the above advantages.
【0028】[0028]
【実施例】以下、実施例および比較例により本発明をさ
らに詳しく説明する。The present invention will be described below in more detail with reference to Examples and Comparative Examples.
【0029】実施例1 20〜42メッシュに整粒したガンマー・アルミナ25
gを秤量した。次に塩化白金酸を白金として1重量%担
持できるように秤量し、水に溶解させて25ccの水溶
液とした。この水溶液にガンマー・アルミナを浸漬し、
ロータリー・エバポレータを用いて湯浴上で蒸発させ乾
燥させた。さらに500℃で焼成後、400℃で2時間
水素還元したものを1重量%のPt/Al2 O3 触媒と
して使用した。Example 1 Gamma-alumina 25 sized to 20-42 mesh
g was weighed. Next, chloroplatinic acid was weighed so as to carry 1% by weight of platinum, and dissolved in water to obtain a 25 cc aqueous solution. Immerse gamma alumina in this aqueous solution,
Evaporate and dry on a hot water bath using a rotary evaporator. After calcination at 500 ° C., hydrogen reduced at 400 ° C. for 2 hours was used as a 1 wt% Pt / Al 2 O 3 catalyst.
【0030】得られたPt/Al2 O3 触媒11.3g
を固定床流通型反応装置の10mm径反応管に充填し、
1容量%の水素を含有するCOガスをW/F(触媒重量
をガス流量で割った値)15g・h/モルの割合で該触
媒層に通し、表1に示した条件下にメタン化反応を行な
って水素含有COガス中の水素含有量を低減させる実験
を行ったところ表1に示した結果が得られた。11.3 g of the obtained Pt / Al 2 O 3 catalyst
Into a 10 mm diameter reaction tube of a fixed bed flow type reactor,
CO gas containing 1% by volume of hydrogen was passed through the catalyst layer at a rate of 15 g · h / mol (W / F (catalyst weight divided by gas flow rate)), and the methanation reaction was conducted under the conditions shown in Table 1. Was performed to reduce the hydrogen content in the hydrogen-containing CO gas, and the results shown in Table 1 were obtained.
【0031】実施例態2〜3 実施例1と同様にして、Pd/Al2O3触媒(実施例
2)およびRh/Al2O3触媒(実施例3)を得、そ
れぞれの触媒について、表1に示した条件下、実施例1
と同様の実験を行なった。得られた結果を表1に示す。Examples 2 to 3 In the same manner as in Example 1, a Pd / Al 2 O 3 catalyst (Example 2) and a Rh / Al 2 O 3 catalyst (Example 3) were obtained. Example 1 under the conditions shown in Table 1.
The same experiment was performed. Table 1 shows the obtained results.
【0032】実施例態4 担体として活性炭を使用し、焼成工程を省略した以外実
施例1と同様にして活性炭担体Rh触媒を調製した。該
触媒を用い表1に示した条件下実施例1と同様の実験を
行なった。得られた結果を表1に示す。Example 4 An activated carbon carrier Rh catalyst was prepared in the same manner as in Example 1 except that activated carbon was used as the carrier and the calcination step was omitted. The same experiment as in Example 1 was conducted using the catalyst under the conditions shown in Table 1. Table 1 shows the obtained results.
【0033】比較例1 硝酸アルミニウム、硝酸ニッケルおよび炭酸カリウムを
原料として沈澱を生成し、水洗、乾燥、打錠後、450
℃で焼成し粉砕して20〜42メッシュに整粒して、N
iO70重量%を含有するNiO/Al2O3触媒を調
製した。該触媒を用い、表1に示した条件下、実施例1
と同様の実験を行なった。得られた結果を表1に示す。比較例2 実施例1と同様にして、Ru/Al 2 O 3 触媒を得、表
1に示す条件下、実施例1と同様の実験を行なった。得
られた結果を表1に示す。 Comparative Example 1 A precipitate was formed using aluminum nitrate, nickel nitrate and potassium carbonate as raw materials, washed with water, dried, and tableted.
C. and crushed and sized to 20-42 mesh.
A NiO / Al 2 O 3 catalyst containing 70% by weight of iO was prepared. Example 1 was prepared using the catalyst under the conditions shown in Table 1.
The same experiment was performed. Table 1 shows the obtained results. Comparative Example 2 In the same manner as in Example 1, a Ru / Al 2 O 3 catalyst was obtained.
An experiment similar to that of Example 1 was performed under the conditions shown in FIG. Profit
The results obtained are shown in Table 1.
【0034】[0034]
【表1】 [Table 1]
【0035】参考例1 粒状活性炭(武田薬品工業製白鷺C2C)を20〜42
メッシュ(粒径0.35〜0.84mm)に整粒し、1
5.21g秤量した。次に塩化ロジウムをロジウム金属
として2.5重量%担持できるように秤量し、水に溶解
させて100ccの水溶液とした。この水溶液に活性炭
を浸漬し、ロータリーエボパレータを用いて湯浴上で蒸
発させ、さらに乾燥器で120℃で乾燥させた。これを
400℃で2時間水素で還元させたものを触媒として使
用した。 Reference Example 1 Granular activated carbon (Shirasagi C2C, manufactured by Takeda Pharmaceutical Co., Ltd.)
After sizing to a mesh (particle size 0.35 to 0.84 mm),
5.21 g were weighed. Next, rhodium chloride was weighed so as to carry 2.5% by weight of rhodium metal as a metal, and dissolved in water to obtain a 100 cc aqueous solution. Activated carbon was immersed in this aqueous solution, evaporated on a hot water bath using a rotary evaporator, and further dried at 120 ° C. in a drier. This was reduced with hydrogen at 400 ° C. for 2 hours and used as a catalyst.
【0036】反応装置として、原料ガスとメタノール供
給機器、メタノール蒸発器、原料予熱器、反応器(内径
10mm)、冷却器および酢酸回収器から構成される固
定床流通型反応装置を用いた。あらかじめ99.95%
の純度に精製された高純度COガスおよびそれに水素を
混合してそれぞれ水素濃度、0.5容量%、1容量%お
よび2容量%の原料ガスを調製した。As the reactor, a fixed bed flow type reactor comprising a raw material gas and methanol supply equipment, a methanol evaporator, a raw material preheater, a reactor (inner diameter: 10 mm), a cooler and an acetic acid collector was used. 99.95% in advance
Was mixed with high-purity CO gas purified to a purity of 0.5% to prepare a raw material gas having a hydrogen concentration of 0.5% by volume, 1% by volume and 2% by volume, respectively.
【0037】メタノールとヨウ化メチルは一定流量で蒸
発器に供給し気化させ、さらに原料ガスを一定流量で混
合して原料予熱器で混合原料を160℃に昇温後、活性
炭担体ロジウム金属触媒6gを充填した反応器に導入し
た。反応器から出た生成物は冷却して気液分離により酢
酸を回収した。反応条件は以下の通りである。 反応温度 200℃ 反応圧力 9kg/cm2 G W/F(触媒重量を原料液量で割った数値)=15g・
h/mol CO(水素を含む):メタノール:ヨウ化メチル=10
0:20:1(モル比)Methanol and methyl iodide are supplied to an evaporator at a constant flow rate to be vaporized. Further, raw material gases are mixed at a constant flow rate, and the mixed raw material is heated to 160 ° C. by a raw material preheater. Was introduced into the reactor. The product discharged from the reactor was cooled and acetic acid was recovered by gas-liquid separation. The reaction conditions are as follows. Reaction temperature 200 ° C. Reaction pressure 9 kg / cm 2 GW / F (a value obtained by dividing the weight of the catalyst by the amount of the raw material liquid) = 15 g ·
h / mol CO (including hydrogen): methanol: methyl iodide = 10
0: 20: 1 (molar ratio)
【0038】得られた結果を表2および図1に示す。The results obtained are shown in Table 2 and FIG.
【0039】比較例3 表2に示した条件下、参考例1と同様の実験を行なっ
た。得られた結果を表2および図1に示す。Comparative Example 3 The same experiment as in Reference Example 1 was performed under the conditions shown in Table 2. The results obtained are shown in Table 2 and FIG.
【0040】[0040]
【表2】 [Table 2]
【0041】参考例2 表3に示す条件下、参考例1と同様の実験を行なった。
得られた結果を表3に示す。 Reference Example 2 The same experiment as in Reference Example 1 was performed under the conditions shown in Table 3.
Table 3 shows the obtained results.
【0042】[0042]
【表3】 [Table 3]
【0043】比較例4 塩化ロジウムの代りに酢酸ニッケルを使用してニッケル
を金属として2.5重量%担持してなる活性炭担体ニッ
ケル触媒を調製し、該触媒を用いる以外参考例1と同様
の実験を行なった。その結果、活性炭担体ロジウム金属
触媒と比較して原料CO中水素が0容量%では酢酸収率
が9.6容量%と低かった(メタン副生率0.63
%)。また、水素9.4容量%の場合には酢酸収率が3
8.8%と向上したものの活性炭担体ロジウム金属触媒
の結果より低く、かつメタンの生成が3.33%に増加
した。Comparative Example 4 An experiment similar to that of Reference Example 1 was carried out except that nickel acetate was used in place of rhodium chloride to prepare a nickel catalyst supporting 2.5% by weight of nickel as a metal, and this catalyst was used. Was performed. As a result, as compared with the activated carbon carrier rhodium metal catalyst, the acetic acid yield was as low as 9.6% by volume when the hydrogen content in the raw material CO was 0% by volume (methane by-product rate was 0.63%).
%). In the case of 9.4% by volume of hydrogen, the acetic acid yield is 3%.
Although improved to 8.8%, it was lower than the result of the activated carbon supported rhodium metal catalyst, and methane production increased to 3.33%.
【図1】参考例1および比較例3におけるCOガス中の
水素含有量と酢酸の収率との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the hydrogen content in CO gas and the yield of acetic acid in Reference Example 1 and Comparative Example 3 .
【図2】前記酢酸製造方法の1例を示すフローチャート
図である。2 is a flowchart showing an example of the acetic acid production process.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C10K 1/34 C10K 1/34 (58)調査した分野(Int.Cl.6,DB名) C10K 3/02 C10K 1/34 C01B 31/18──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 identification code FI C10K 1/34 C10K 1/34 (58) Investigated field (Int.Cl. 6 , DB name) C10K 3/02 C10K 1/34 C01B 31/18
Claims (3)
る群から選ばれた白金族系金属を耐熱性担体に担持して
なる触媒を充填した反応器に、水素含有COガスを導入
させ、一定条件下接触的にメタン化反応を行わせて該ガ
ス中に含まれる水素を除去することを特徴とする水素含
有COガスの精製方法。1. A method comprising platinum, palladium and rhodium.
A hydrogen-containing CO gas was introduced into a reactor filled with a catalyst comprising a platinum group metal supported on a heat-resistant carrier selected from the group consisting of: A method for purifying hydrogen-containing CO gas, comprising removing hydrogen contained in the gas.
載の水素含有COガスの精製方法。2. The method for purifying a hydrogen-containing CO gas according to claim 1, wherein said platinum group metal is platinum.
る請求項1記載の水素含有COガスの精製方法。3. The method for purifying a hydrogen-containing CO gas according to claim 1, wherein said heat-resistant carrier is gamma-alumina.
Priority Applications (1)
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JP3175817A JP2756736B2 (en) | 1991-06-21 | 1991-06-21 | Method for purifying hydrogen-containing CO gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3175817A JP2756736B2 (en) | 1991-06-21 | 1991-06-21 | Method for purifying hydrogen-containing CO gas |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05994A JPH05994A (en) | 1993-01-08 |
JP2756736B2 true JP2756736B2 (en) | 1998-05-25 |
Family
ID=16002749
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JP3175817A Expired - Lifetime JP2756736B2 (en) | 1991-06-21 | 1991-06-21 | Method for purifying hydrogen-containing CO gas |
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