JP2010270122A - アクロレインをアクリル酸にする不均一触媒作用気相酸化方法及び管束反応器 - Google Patents
アクロレインをアクリル酸にする不均一触媒作用気相酸化方法及び管束反応器 Download PDFInfo
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- JP2010270122A JP2010270122A JP2010148547A JP2010148547A JP2010270122A JP 2010270122 A JP2010270122 A JP 2010270122A JP 2010148547 A JP2010148547 A JP 2010148547A JP 2010148547 A JP2010148547 A JP 2010148547A JP 2010270122 A JP2010270122 A JP 2010270122A
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- catalyst
- gas
- tube
- heat treatment
- acrolein
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 15
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
【解決手段】この課題は、触媒の活物質が特定の熱処理方法により製造された特定の多元素酸化物質である、アクロレインをアクリル酸にする不均一触媒作用気相酸化方法、及び、特定の本数の触媒管を有する管束反応器であって、その触媒管は装填物で充填されており、その触媒が活物質として前駆物質を特定の熱処理方法により製造された特定の多元素酸化物質を含有し、この際アクロレインをアクリル酸にする部分酸化に関連する触媒管の装填は、無作為にサンプリングされた12本の触媒管において特定の状態にされており、その際、触媒管装填物の活性の尺度として特定の塩浴が有すべき温度が使用される、管束反応器により解決された。
【選択図】なし
Description
a)少なくとも1個の循環ガスコンプレッサー(13);
b)少なくとも1個の排ガスコンプレッサー(17);
c)少なくとも1個の減圧装置(15);
d)少なくとも1個の新鮮ガス供給管((20)、(21));
e)少なくとも1個の加熱可能な回転管(1);及び
f)少なくとも1個の循環ガス導管。
−熱処理のどの時点でも O2 0.5〜4容量%、
−還元性熱処理の全期間に渡り平均して NH3 1〜8容量%並びに
−残分量としての水蒸気及び/又は不活性ガス
を含有するものであり、この際、熱処理の間の雰囲気のNH3−含有率は、20容量%を下回る最大を経過する。
Mo12VaX1 bX2 cX3 dX4 eX5 fX6 gOn (I)
[式中、変数は次のものを意味する:
X1= W、Nb、Ta、Cr及び/又はCe、
X2= Cu、Ni、Co、Fe、Mn及び/又はZn、
X3= Sb及び/又はBi、
X4= 1種以上のアルカリ金属(Li、Na、K、Rb、Cs)及び/又はH、
X5= 1種以上のアルカリ土類金属(Mg、Ca、Sr、Ba)、
X6= Si、Al、Ti及び/又はZr、
a = 1〜6、
b = 0.2〜4、
c = 0〜18、有利には0.5〜18、
d = 0〜40、
e = 0〜2、
f = 0〜4、
g = 0〜40 及び
n = I中の酸素とは異なる元素の原子価数及び度数により決まる数値であり、かつ
この際、変数は、前記の範囲内で次の前提で選択されるべきである:
多元素酸化物質(I)の酸素とは異なる全ての元素の全量に対する元素Moのモル割合は20モル%〜80モル%であり、触媒活性多元素酸化物質(I)中に含有しているMoと触媒活性多元素酸化物質(I)中に含有しているVとのモル比Mo/Vは15:1〜1:1であり、相応するモル比Mo/(WとNbとからの合計量)は80:1〜1:4である(かつ、多元素酸化物質がCuを含有する場合には、相応するモル比Mo/Cuは30:1〜1:3である)]。
X1= W、Nb及び/又はCr、
X2= Cu、Ni、Co及び/又はFe、
X3= Sb、
X4= Na及び/又はK、
X5= Ca、Sr及び/又はBa、
X6= Si、Al及び/又はTi、
a = 2.5〜5、
b = 0.5〜2、
c = 0.5〜3、
d = 0〜2、
e = 0〜0.2、
f = 0〜1、
g = 0〜15 及び
n = I中の酸素とは異なる元素の原子価数及び度数により決まる数値である。
Mo12VaX1 bX2 cX5 fX6 gOn (II)
[式中、変数は次のものを意味する:
X1= W及び/又はNb、
X2= Cu及び/又はNi、
X5= Co及び/又はSr、
X6= Si及び/又はAl、
a = 3〜4.5、
b = 1〜1.5、
c = 0.75〜2.5、
f = 0〜0.5、
g = 0〜8 及び
n = II中の酸素とは異なる元素の原子価数及び頻度により決まる数値であり、かつ
この際、変数は、前記の範囲内で次の前提で選択されるべきである:多元素酸化物活物質(II)の酸素とは異なる全ての元素の全量に対する元素Moのモル割合は20モル%〜80モル%であり、触媒活性多元素酸化物質(II)中に含有しているMoと触媒活性多元素酸化物質(II)中に含有しているVとのモル比Mo/Vは15:1〜1:1であり、相応するモル比Mo/Cuは30:1〜1:3であり、かつ、相応するモル比Mo/(WとNbとからの合計量)は80:1〜1:4である]。
「本発明により必要であるか焼雰囲気は、簡単に例えば、O2、NH3及び不活性ガス/水蒸気に関して適当な組成を有するガス混合物が導通される炉内でか焼することにより実現化することができる。有利性の低い1実施形では、このか焼雰囲気の必要な平均アンモニア含有率は、か焼すべき乾燥物質中に適当な量のアンモニウムイオン(これはか焼の経過でNH3−排ガス下に分解する)を導入することによっても達成することができる。」
EP−B724481においてか焼が循環空気炉内で実施された場合には、これに、特に特定の容量割合のNH3(容量%)を含有するガス混合物が供給された。
Mo1VbM1 cM2 d (III)
[式中、
M1 =Te及び/又はSb、
M2 =Nb、Ta、W、Ti、Al、Zr、Cr、Mn、Ga、Fe、Ru、Co、Rh、Ni、Pd、Pt、La、Bi、Ce、Sn、Zn、Si、Na、Li、K、Mg、Ag、Au及びInを包含する群の元素からの少なくとも1種、
b=0.01〜1、 c=>0〜1 及びd=>0〜1 ]。
Mo1VbM1 cM2 dOn (IV)
[式中、変数は、化学量論式IIIに関して示されている意味を有し、nは(IV)中の酸素とは異なる元素の原子価数及び度数により決められる数である]。
R=P√(P1+Pk)
により定義される強度割合であるものを得るために全く特別に好適である。前記のX線回折図は、その最大が2θ=50±0.3°にある回折反射を有しないのが有利である。
9.0±0.4°(l)
6.7±0.4°(o)及び
7.9±0.4°(p)。
i: 5〜95、屡々5〜80、部分的には10〜60、
l: 1〜30;
m: 1〜40;
n: 1〜40;
o: 1〜30;
p: 1〜30及び
q: 5〜60。
A)化学量論式Mo12V3W1.2Cu2.4Oxの多元素酸化物質を得る目的の前駆物質の製造
酢酸銅(II)水和物(CuO含有率:40.0質量%)16.3kgを、温度25℃の水274リットル中に撹拌下に溶かした。澄明溶液1が得られた。
熱処理の実施を、この明細書中に例示されている実施形による規模及び補助手段を有する図1における回転管炉装置中で、かつ次の条件下に行った:
− 熱処理を、A)に記載のようにして製造された材料量300kgを用いて回分法で行った;
− 水平に対する回転管の傾斜角度は約0°であった;
− 回転管を、1.5回/minで右回転させた;
− 全体の熱処理の間に、この回転管に、(当初に含有されている空気の排除の後に)次のような組成を有するガス流205Nm3/hを供給し、この回転管の出口から更なるシーリングガス窒素25Nm3/hを補充した:
ベース負荷−窒素(20)及び回転管内で発生したガスの組成物 80Nm3/h、
シーリングガス窒素(11) 25Nm3/h、
空気(スプリッター(21)) 30Nm3/h及び
再循環される循環ガス(19) 70Nm3/h。
− 10時間かかって、この材料温度を25℃から実質的に直線的に300℃まで加熱し;
引き続き、この材料温度を2時間かかって実質的に直線的に360℃まで加熱し;
その後、この材料温度を7時間かかって実質的に直線的に350℃まで低下させ;
次いで、この材料温度を2時間かかって実質的に直線的に420℃まで高め、かつこの材料温度を30分間保持し;
− 次いで、この回転管に供給されたガス流中で空気30Nm3/hを、相応して上昇するベース負荷−窒素で交換し(これにより特有の熱処理の経過が終了した)、回転管の加熱を中断し、かつ材料を、環境空気の吸引による回転管の急速冷却の接続によって2時間かかって100℃を下回る温度まで、かつ最後に環境温度まで冷却させ;この場合にこのガス流を25℃の温度で回転管に供給した;
−全体の熱処理の間に、ガス流の回転管出口の(直)後の圧力は、外圧を0.2ミリバール下回っていた。
B)で得られた触媒活性物質を、バイプレックス交叉流か焼ミル(BQ500)(Fa.Hosokawa-Alpine Augsburg)を用いて粉砕して、微細粉末にした(その粉末粒子の50%は、1〜10μの目幅の篩を通過し、50μmを上まわる縦寸法を有する粒子分は1%より少なかった)。
シェル触媒を、次のように、塩浴(硝酸カリウム53質量%、亜硝酸ナトリウム40質量%及び硝酸ナトリウム7質量%からの混合物)で包囲流過されるモデル触媒管中で試験した:
モデル触媒管: V2A−鋼、壁厚2mm、内径26mm、外径4mmのサーモスリーブ(サーモカップルの収納のため)を中央に有し、このモデル触媒管の自由空間1.56リットルにシェル触媒を充填した。
アクロレイン4.8容量%、酸素7容量%、水蒸気10容量%、窒素78.2容量%。
全体を実施例1と同様に実施した。しかしながら、多金属酸化物活物質の成形を次のように行った:
リング形担体(外径7.1mm、長さ3.2mm、内径4.0mm;表面粗面性Rz45μm及び担体の容積に対する孔全容積≦1容量%を有するFa.Ceram TecのC220型のステアタイト)70kgを、内容積200リットルのコーティングパン(傾斜角度90°;Fa.Loedige,DEのHicoater)中に充填した。引き続き、このコーティングパンを16U/minで回転させた。ノズルから25分かかって水75質量%及びグリセリン25質量%からの水溶液3.8〜4.2リットルをこの担体上に吹き付けた。同時に、同じ時間に渡り粉砕された多金属酸化物活物質(この比表面積は13.8m2/gであった)の18.1kgを、振動トラフからアトマイザーノズルのスプレーコーンの外側に連続的に配量添加した。この被覆の間に、供給された粉末は、完全に担体の表面上に吸収され、微細な酸化物活物質の凝集は観察されなかった。活物質粉末及び水の添加の終了後に、2U/minの回転速度で40分間(選択的に15〜60分)、100℃(選択的に80〜120℃)の熱空気(約400m3/min)を、このコーティングパン中に吹き込んだ。全質量に対する酸化物活物質の割合20質量%を有するリング形シェル触媒が得られた。1担体の表面上でも種々の担体の表面上でもシェル厚さは170±50μmであった。
全てを実施例1と同様に実施した。しかしながら、多金属酸化物活物質の成形を次のように行った:
球形担体(直径4〜5mm;45μmの表面粗面性Rz及び担体の容積に対する孔全容積≦1容量%を有するFa.Ceram TecのC220型のステアタイト)70kgを、200リットル内容積のコーティングパン(傾斜角度90°;Fa.Loedige、DEのHicoater)中に充填した。引き続き、このコーティングパンを16U/minで回転させた。ノズルから25分かかって水2.8〜3.3リットルを、この担体上に吹き付けた。同時に同じ時間に渡り、粉砕された多金属酸化物活物質14.8kgを振動トラフからアトマイザーノズルのスプレーコーンの外側に連続的に配量添加した。この被覆の間に、供給された粉末は完全に担体の表面上に吸収され、微細な酸化物活物質の凝集は観察されなかった。粉末及び水の添加終了の後に、2U/minの回転速度で40分(選択的に15〜60分)、100℃(選択的に80〜120℃)の熱空気(約400m3/min)をこのコーティングパン中に吹き込んだ。その酸化物活物質分が全物質に対して17質量%である球形シェル触媒が得られた。1担体の表面上にも種々の担体の表面上にも認められるシェル厚さは、160±50μmであった。
Claims (3)
- 触媒の活物質が、
元素Nb及びWの少なくとも1種並びに元素Mo及びVを含有する多元素酸化物質であり、この際、触媒活性物質の酸素とは異なる全ての元素の合計量に対する元素Moのモル割合は20モル%〜80モル%であり、触媒活性多元素酸化物質中に含有しているMoと触媒活性多元素酸化物質中に含有しているVとのモル比Mo/Vは15:1〜1:1であり、相応するモル比Mo/(WとNbとからの合計量)は80:1〜1:4であり、かつ、ガス流により流過される回転管炉内で300〜450℃の材料温度で、O2及びNH3を含有するガス雰囲気中で熱処理する方法により製造されており、その際、
−前駆物質として、多元素酸化物質の酸素とは異なる元素構成物を成分として含有する出発化合物から、アンモニウムイオンをも含有する緊密な乾燥混合物を製造し、
−その中で熱処理が行われるガス雰囲気は、
−どの時点でも O2 0.5〜4容量%、
−還元性熱処理の全期間に渡り平均して NH3 1〜8容量%並びに
−残分量としての水蒸気及び/又は不活性ガス
を含有するものであり、
−熱処理の間の雰囲気のNH3−含有率は、20容量%を下回る最大を経過し、かつ、
−回転管炉を流過するガス流の少なくとも一部分量を循環させ、かつNH3の外からの添加を行わない
ことを特徴とするアクロレインをアクリル酸にする不均一触媒作用気相酸化方法。 - 5000〜40000本の触媒管を有する管束反応器であって、その触媒管は装填物で充填されており、その触媒が活物質として多元素酸化物質を含有し、該物質は、元素Nb及びWの少なくとも1種並びに元素Mo及びVを含有し、この際、触媒活性多元素酸化物質の酸素とは異なる全ての元素の合計量に対する元素Moのモル割合は20モル%〜80モル%であり、触媒活性多元素酸化物質中に含有しているMoと触媒活性多元素酸化物中に含有しているVとのモル比Mo/Vは15:1〜1:1であり、相応するモル比Mo/(WとNbとからの合計量)は80:1〜1:4であり、かつ前記多元素酸化物質は、請求項1に記載の熱処理する方法で得られ、この際アクロレインをアクリル酸にする部分酸化に関連する触媒管の装填は、無作為にサンプリングされた12本の触媒管において算術平均活性と最大活性又は最小活性との間の差が8℃を上まわらないような状態にされており、その際、触媒管装填物の活性の尺度として、個々の触媒管の周りに通される、硝酸カリウム53質量%、亜硝酸ナトリウム40質量%及び硝酸ナトリウム7質量%からの塩浴が有すべき温度が使用され、従って、アクロレイン4.8容量%、酸素7容量%、水蒸気10容量%及び窒素78.2容量%からの反応ガス混合物の1回流過の場合、アクロレイン85Nl/触媒装填物l×hでの触媒装填物の負荷の場合に、この装填された触媒管によって97モル%のアクロレイン変換率が得られる、管束反応器。
- ≧135Nl/l・hの触媒装填物のアクロレイン負荷で作動される、請求項2に記載の管束反応器。
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DE2003125487 DE10325487A1 (de) | 2003-06-04 | 2003-06-04 | Verfahren zur thermischen Behandlung der Vorläufermasse einer katalytischen Aktivmasse |
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KR101350877B1 (ko) * | 2012-03-19 | 2014-01-16 | 한화케미칼 주식회사 | 해압 장치를 이용한 전극 활물질의 제조 |
CN110243170A (zh) * | 2019-06-17 | 2019-09-17 | 蚌埠兴创电子科技有限公司 | 一种不锈钢钎焊烧结炉 |
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DE102006036177B4 (de) * | 2006-07-21 | 2013-05-08 | Evonik Degussa Gmbh | Vorrichtung und Verfahren zur Herstellung von Acrylsäure mit verminderter Autoxidationsneigung |
DE102007010422A1 (de) | 2007-03-01 | 2008-09-04 | Basf Se | Verfahren zur Herstellung eines Katalysators bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Masse |
DE102007025869A1 (de) | 2007-06-01 | 2008-07-03 | Basf Se | Verfahren der Wiederbeschickung der Reaktionsrohre eines Rohrbündelreaktors mit einem neuen Katalysatorfestbett |
DE102007028333A1 (de) | 2007-06-15 | 2008-12-18 | Basf Se | Verfahren zum Einbringen einer wenigstens einer Produktionscharge von ringförmigen Schalenkatalysatoren K entnommenen Teilmenge in ein Reaktionsrohr eines Rohrbündelreaktors |
TW200948474A (en) | 2008-04-09 | 2009-12-01 | Basf Se | Coated catalysts comprising a multimetal oxide comprising molybdenum |
DE102011076931A1 (de) | 2011-06-03 | 2012-12-06 | Basf Se | Wässrige Lösung, enthaltend Acrylsäure und deren konjugierte Base |
DE102013202048A1 (de) | 2013-02-07 | 2013-04-18 | Basf Se | Verfahren zur Herstellung einer katalytisch aktiven Masse, die ein Gemisch aus einem die Elemente Mo und V enthaltenden Multielementoxid und wenigstens einem Oxid des Molybdäns ist |
JP6922993B2 (ja) * | 2017-10-20 | 2021-08-18 | 三菱ケミカル株式会社 | α,β−不飽和カルボン酸製造用触媒の製造方法、α,β−不飽和カルボン酸の製造方法、及びα,β−不飽和カルボン酸エステルの製造方法 |
EP3770145A1 (en) | 2019-07-24 | 2021-01-27 | Basf Se | A process for the continuous production of either acrolein or acrylic acid as the target product from propene |
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