TWI774969B - Method for producing methacrolein and/or methacrylic acid - Google Patents
Method for producing methacrolein and/or methacrylic acid Download PDFInfo
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- 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
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Abstract
本發明提供一種甲基丙烯醛及/或甲基丙烯酸之選擇率優異之甲基丙烯醛及/或甲基丙烯酸之製造方法。 本發明係一種甲基丙烯醛及/或甲基丙烯酸之製造方法,其包括:將含氧氣體與包含異丁烯及第三丁醇中之至少一者之氣體加以混合而獲得混合氣體之步驟、及將上述混合氣體於100~200℃之溫度下供給至具備氧化觸媒之反應器之步驟。The present invention provides a method for producing methacrolein and/or methacrylic acid having excellent selectivity of methacrolein and/or methacrylic acid. The present invention relates to a method for producing methacrolein and/or methacrylic acid, which comprises the steps of mixing an oxygen-containing gas with a gas containing at least one of isobutylene and tertiary butanol to obtain a mixed gas, and The step of supplying the above-mentioned mixed gas to a reactor equipped with an oxidation catalyst at a temperature of 100 to 200°C.
Description
本發明係關於一種甲基丙烯醛及/或甲基丙烯酸之製造方法。The present invention relates to a method for producing methacrolein and/or methacrylic acid.
作為甲基丙烯醛及/或甲基丙烯酸之製造方法,例如已知有使用異丁烯之方法(例如參照專利文獻1~4)。 [先前技術文獻] [專利文獻]As a method for producing methacrolein and/or methacrylic acid, for example, a method using isobutylene is known (for example, refer to Patent Documents 1 to 4). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2002-53519號公報 [專利文獻2]日本專利特開2005-314314號公報 [專利文獻3]日本專利特開2004-277339號公報 [專利文獻4]日本專利特公昭60-25195號公報[Patent Document 1] Japanese Patent Laid-Open No. 2002-53519 [Patent Document 2] Japanese Patent Laid-Open No. 2005-314314 [Patent Document 3] Japanese Patent Laid-Open No. 2004-277339 [Patent Document 4] Japanese Patent Publication No. 60-25195
[發明所欲解決之問題][Problems to be Solved by Invention]
於甲基丙烯醛及/或甲基丙烯酸之製造方法中,要求以較高之選擇率獲得甲基丙烯醛及/或甲基丙烯酸。因此,本發明之目的在於提供一種可以優異之選擇率製造甲基丙烯醛及/或甲基丙烯酸之甲基丙烯醛及/或甲基丙烯酸之製造方法。 [解決問題之技術手段]In the production method of methacrolein and/or methacrylic acid, it is required to obtain methacrolein and/or methacrylic acid with high selectivity. Therefore, the objective of this invention is to provide the manufacturing method of methacrolein and/or methacrylic acid which can manufacture methacrolein and/or methacrylic acid with excellent selectivity. [Technical means to solve problems]
本發明之甲基丙烯醛及/或甲基丙烯酸之製造方法包括:將含氧氣體與包含異丁烯及第三丁醇中之至少一者之氣體加以混合而獲得混合氣體之步驟、及將上述混合氣體於100~200℃之溫度下供給至具備氧化觸媒之反應器之步驟。The method for producing methacrolein and/or methacrylic acid of the present invention includes the steps of mixing an oxygen-containing gas and a gas containing at least one of isobutylene and tertiary butanol to obtain a mixed gas, and mixing the above The step of supplying the gas to a reactor equipped with an oxidation catalyst at a temperature of 100 to 200°C.
根據上述方法,可以優異之選擇率製造甲基丙烯醛及/或甲基丙烯酸。According to the above method, methacrolein and/or methacrylic acid can be produced with excellent selectivity.
於上述方法中,較佳為獲得混合氣體之步驟包括:藉由稀釋氣體稀釋含氧氣體之步驟、及將經稀釋之含氧氣體與包含異丁烯及第三丁醇中之至少一者之氣體加以混合之步驟。In the above method, preferably the step of obtaining the mixed gas comprises: the step of diluting the oxygen-containing gas with a diluent gas, and adding the diluted oxygen-containing gas to a gas containing at least one of isobutylene and tertiary butanol. mixing steps.
根據上述方法,可進一步提高甲基丙烯醛及/或甲基丙烯酸之選擇率。According to the above method, the selectivity of methacrolein and/or methacrylic acid can be further improved.
於上述方法中,較佳為反應器具備氧化觸媒之填充層,供給至反應器之混合氣體之溫度低於填充層之出口之氣體溫度,出口之氣體溫度與供給至反應器之混合氣體之溫度之差為120℃以上。In the above method, it is preferable that the reactor is provided with a packed layer of oxidation catalyst, the temperature of the mixed gas supplied to the reactor is lower than the temperature of the gas at the outlet of the packed layer, and the temperature of the gas at the outlet is different from that of the mixed gas supplied to the reactor. The difference in temperature is 120°C or more.
根據上述方法,可進一步提高甲基丙烯醛及/或甲基丙烯酸之選擇率。According to the above method, the selectivity of methacrolein and/or methacrylic acid can be further improved.
於上述方法中,較佳為反應器具備氧化觸媒之填充層及向反應器供給熱媒而調整填充層之溫度之溫度調整機構,供給至反應器之混合氣體之溫度低於供給至反應器之熱媒之溫度,供給至反應器之熱媒之溫度與供給至反應器之混合氣體之溫度之差為120℃以上。In the above method, it is preferable that the reactor is provided with a packed layer of an oxidation catalyst and a temperature adjustment mechanism for supplying a heat medium to the reactor to adjust the temperature of the packed layer, and the temperature of the mixed gas supplied to the reactor is lower than that supplied to the reactor. The temperature of the heat medium, the difference between the temperature of the heat medium supplied to the reactor and the temperature of the mixed gas supplied to the reactor is 120°C or more.
根據上述方法,可進一步提高甲基丙烯醛及/或甲基丙烯酸之選擇率。 [發明之效果]According to the above method, the selectivity of methacrolein and/or methacrylic acid can be further improved. [Effect of invention]
根據本發明,可提供一種可以優異之選擇率製造甲基丙烯醛及/或甲基丙烯酸之甲基丙烯醛及/或甲基丙烯酸之製造方法。According to the present invention, a method for producing methacrolein and/or methacrylic acid capable of producing methacrolein and/or methacrylic acid with excellent selectivity can be provided.
於本說明書中,異丁烯係指2-甲基丙烯。In this specification, isobutene refers to 2-methylpropene.
以下,說明本發明之一實施形態之甲基丙烯醛及/或甲基丙烯酸之製造方法。
首先,參照圖1,對本實施形態之甲基丙烯醛及/或甲基丙烯酸之製造裝置100進行說明。Hereinafter, a method for producing methacrolein and/or methacrylic acid according to one embodiment of the present invention will be described.
First, with reference to FIG. 1, the
該製造裝置100具備:包含異丁烯及第三丁醇(亦稱為「TBA」)中之至少一者之氣體(以下亦稱為「原料氣體」)之供給源、含氧氣體之供給源、水蒸氣之供給源、氣體混合機50a、第一反應器10、第二反應器20、分離機構60、氣體燃燒機構80、溫度調整機構52、氣體混合機50b及壓縮機55。The
原料氣體之供給源及含氧氣體之供給源分別經由管線L2及管線L1連接至氣體混合機50a。水蒸氣之供給源經由管線L4連接至管線L1。氣體混合機50a經由管線L10連接至第一反應器10。The supply source of the raw material gas and the supply source of the oxygen-containing gas are connected to the gas mixer 50a via the line L2 and the line L1, respectively. A supply source of water vapor is connected to line L1 via line L4. The gas mixer 50a is connected to the
第一反應器10經由管線L21連接至第二反應器20。於管線L21設置有氣體混合機50b,氧氣之供給源經由壓縮機55及管線L22連接至氣體混合機50b。The
第二反應器20經由管線L30連接至分離機構60。於分離機構60之上部連接有管線L35,於下部連接有管線L31,於側面連接有管線L23。管線L23連接至管線L21之第一反應器10與氣體混合機50b之間之位置。管線L35連接至氣體燃燒機構80。氣體燃燒機構80經由管線L38連接至溫度調整機構52,溫度調整機構52經由管線L3連接至管線L1。管線L3與管線L1之連接部係管線L1及管線L4之連接部與含氧氣體之供給源之間之位置。The
第一反應器10具備熱媒之供給管線L101及熱媒之排出管線L102。第一反應器10具備氧化觸媒。作為該氧化觸媒,例如可列舉:包含鉬及鉍之金屬氧化物。The
第一反應器10較佳為容器內填充有氧化觸媒之反應器。即,第一反應器10較佳為具備氧化觸媒之填充層(以下亦稱為「觸媒填充層」)。第一反應器10可為容器內填充有氧化觸媒之固定床反應裝置。又,第一反應器10較佳為具備向第一反應器10供給熱媒而調整觸媒填充層之溫度之溫度調整機構。第一反應器10可為具備上述溫度調整機構之多管式管型反應器。熱媒及反應流之朝向無限制,可為上升流亦可為下降流。The
分離機構60之例為蒸餾塔。An example of the
氣體燃燒機構80係燃燒氣體之裝置。氣體燃燒機構80亦可具備觸媒。The
溫度調整機構52之例為熱交換器。An example of the
第二反應器20具備熱媒之供給管線L103、及熱媒之排出管線L104。第二反應器20具備氧化觸媒。作為該氧化觸媒,例如可列舉:包含磷及鉬之雜多酸化合物。The
第二反應器20較佳為容器內填充有氧化觸媒之反應器。第二反應器20可為容器內填充有氧化觸媒之固定床反應裝置。第二反應器20較佳為具備溫度調整機構之多管式管型反應器。熱媒及反應流之朝向無限制,分別可為上升流亦可為下降流。即,熱媒及反應流之流動方向可為對流、平流、錯流中之任一者。The
繼而,對本實施形態之甲基丙烯醛及/或甲基丙烯酸之製造方法進行說明。Next, the manufacturing method of the methacrolein and/or methacrylic acid of this embodiment is demonstrated.
(供給源) 首先,準備作為原料氣體之供給源之原料氣體之流(F2)。又,準備作為含氧氣體之供給源之含氧氣體之流(F0)、及作為水蒸氣之供給源之水蒸氣之流(F4)。(supply source) First, the flow (F2) of the raw material gas as the supply source of the raw material gas is prepared. Furthermore, a flow (F0) of the oxygen-containing gas as a supply source of the oxygen-containing gas and a flow (F4) of the water vapor as a supply source of the water vapor are prepared.
流(F2)亦可包含除異丁烯及TBA以外之成分。作為除異丁烯及TBA以外之成分,例如可列舉:異戊二烯等C5烯烴類、異丁烷、1-丁烯、丙烷、丙烯、正丁烷、甲基第三丁醚、甲醇、二甲醚及丁二烯。Stream (F2) may also contain components other than isobutene and TBA. Examples of components other than isobutylene and TBA include C5 olefins such as isoprene, isobutane, 1-butene, propane, propylene, n-butane, methyl tertiary butyl ether, methanol, and dimethyl ether. ether and butadiene.
流(F2)中之異丁烯及/或TBA之濃度以異丁烯及TBA之濃度之合計,較佳為85~99.99質量%,更佳為90~99.95質量%,進而較佳為95~99.94質量%。The concentration of isobutene and/or TBA in the flow (F2) is preferably 85 to 99.99 mass %, more preferably 90 to 99.95 mass %, and still more preferably 95 to 99.94 mass %, based on the total concentration of isobutene and TBA.
流(F0)亦可包含除氧以外之成分。作為除氧以外之成分,例如可列舉:氮、二氧化碳、一氧化碳、水蒸氣及氬。Stream (F0) may also contain components other than oxygen. Examples of components other than oxygen include nitrogen, carbon dioxide, carbon monoxide, water vapor, and argon.
流(F0)中之氧濃度較佳為15~25體積%,更佳為16~23體積%,進而較佳為18~22體積%。含氧氣體之例為空氣。The oxygen concentration in the flow (F0) is preferably 15-25 vol%, more preferably 16-23 vol%, and still more preferably 18-22 vol%. An example of an oxygen-containing gas is air.
水蒸氣主要包含水。Water vapor mainly contains water.
(混合步驟) 繼而,將含氧氣體之流(F0)及原料氣體之流(F2)分別經由管線L1及管線L2供給至氣體混合機50a。將燃燒氣體(稀釋氣體)之流(F3)經由管線L3供給至管線L1,將水蒸氣(稀釋氣體)之流(F4)經由管線L4供給至管線L1,藉此藉由燃燒氣體及水蒸氣稀釋含氧氣體。即,將含氧氣體之流(F0)與燃燒氣體之流(F3)加以混合而獲得包含氧及燃燒氣體之流(F1)後,將水蒸氣之流(F4)及原料氣體之流(F2)依序混合於流(F1)而獲得混合氣體之流(F10)。(mixing step) Next, the flow (F0) of the oxygen-containing gas and the flow (F2) of the raw material gas are supplied to the gas mixer 50a through the line L1 and the line L2, respectively. The flow (F3) of the combustion gas (diluent gas) is supplied to the line L1 via the line L3, and the flow (F4) of the water vapor (diluent gas) is supplied to the line L1 via the line L4, thereby diluting by the combustion gas and the water vapor Oxygen-containing gas. That is, after mixing the flow of oxygen-containing gas (F0) and the flow of combustion gas (F3) to obtain a flow (F1) containing oxygen and combustion gas, the flow of water vapor (F4) and the flow of raw gas (F2) ) are sequentially mixed in the flow (F1) to obtain the flow (F10) of the mixed gas.
燃燒氣體例如可包含氮、二氧化碳及水。燃燒氣體例如亦可進一步包含一氧化碳、氬等其他成分。The combustion gas may contain nitrogen, carbon dioxide and water, for example. The combustion gas may further contain other components such as carbon monoxide and argon, for example.
混合氣體之流(F10)中之異丁烯及/或TBA之濃度以異丁烯及TBA之濃度之合計,例如為0.5體積%以上、1體積%以上、或2體積%以上。上述濃度以異丁烯及TBA之濃度之合計,例如為10體積%以下、9體積%以下、或8體積%以下。上述濃度以異丁烯及TBA之濃度之合計,較佳為0.5~10體積%,更佳為1~9體積%,進而較佳為2~8體積%。The concentration of isobutene and/or TBA in the mixed gas flow (F10) is, for example, 0.5 vol% or more, 1 vol% or more, or 2 vol% or more based on the total concentration of isobutene and TBA. The above-mentioned concentration is, for example, 10 vol % or less, 9 vol % or less, or 8 vol % or less based on the total concentration of isobutylene and TBA. The above-mentioned concentration is preferably 0.5 to 10% by volume, more preferably 1 to 9% by volume, and still more preferably 2 to 8% by volume based on the total concentration of isobutene and TBA.
流(F10)中之氧濃度例如為6體積%以上、7體積%以上、或8體積%以上。混合氣體中之氧濃度例如為20體積%以下、16體積%以下、或15體積%以下。流(F10)中之氧濃度較佳為6~20體積%,更佳為7~16體積%,進而較佳為8~15體積%。The oxygen concentration in the flow (F10) is, for example, 6 vol % or more, 7 vol % or more, or 8 vol % or more. The oxygen concentration in the mixed gas is, for example, 20 vol % or less, 16 vol % or less, or 15 vol % or less. The oxygen concentration in the flow (F10) is preferably 6 to 20% by volume, more preferably 7 to 16% by volume, and still more preferably 8 to 15% by volume.
流(F10)除上述成分以外,亦可包含氮、水、二氧化碳等其他成分。The flow (F10) may contain other components such as nitrogen, water, and carbon dioxide in addition to the above-mentioned components.
如此,藉由包括藉由稀釋氣體稀釋含氧氣體之步驟、及將經稀釋之含氧氣體與包含異丁烯及第三丁醇中之至少一者之氣體加以混合之步驟,可進一步提高甲基丙烯醛及/或甲基丙烯酸之選擇率。Thus, by including the step of diluting the oxygen-containing gas with the diluent gas, and the step of mixing the diluted oxygen-containing gas with a gas comprising at least one of isobutylene and tertiary butanol, methacrylic acid can be further improved Aldehyde and/or methacrylic acid selectivity.
(供給步驟)
其次,將混合氣體之流(F10)經由管線L10供給至第一反應器10。混合氣體之向第一反應器10之供給溫度為100~200℃。就異丁烯之轉化率之觀點而言,該溫度較佳為105℃以上,更佳為110℃以上,進而較佳為115℃以上。就甲基丙烯醛及/或甲基丙烯酸之選擇率之觀點而言,上述溫度較佳為195℃以下,更佳為190℃以下,進而較佳為185℃以下。(supply step)
Next, the flow (F10) of the mixed gas is supplied to the
混合氣體之向第一反應器10之供給溫度例如可藉由如下方式進行調整,即,藉由鼓風機壓縮含氧氣體之流(F0);調整水蒸氣之流(F4)之溫度及流量;藉由鼓風機壓縮燃燒氣體(稀釋氣體)之流(F3);藉由溫度調整機構52調整流(F3)之溫度;及調整流(F3)之流量。又,亦可於管線L10、管線L1等設置熱交換器等溫度調整機構。The supply temperature of the mixed gas to the
(反應步驟)
於第一反應器10中,由流(F10)中之異丁烯及/或TBA生成甲基丙烯醛,且經由管線L21排出包含甲基丙烯醛之流(F11)。(reaction step)
In the
於原料氣體之流(F2)含有異丁烯之情形時,於第一反應器10內異丁烯與氧反應,藉此生成甲基丙烯醛。When the stream (F2) of the raw material gas contains isobutene, the isobutene reacts with oxygen in the
亦可使用TBA代替異丁烯。於該情形時,由TBA與氧生成甲基丙烯醛。作為具體之反應機構,考慮到藉由TBA之脫水反應生成異丁烯,且生成之異丁烯與氧反應而生成甲基丙烯醛者。認為可使用TBA代替異丁烯之理由在於在第一反應器10內,異丁烯之氧化反應為速率決定步驟。異丁烯與TBA亦可併用。TBA can also be used in place of isobutene. In this case, methacrolein is generated from TBA and oxygen. As a specific reaction mechanism, isobutene is produced by the dehydration reaction of TBA, and the produced isobutene reacts with oxygen to produce methacrolein. The reason for thinking that TBA can be used in place of isobutene is that within the
流(F11)可包含除甲基丙烯醛以外之成分。作為此種成分,例如可列舉:甲基丙烯酸、丙烯醛、丙酮、乙醛、丙醛、對苯二甲酸、順丁烯二酸、反丁烯二酸、雙乙醯、間苯二甲酸、異丁酸、甲基糠醛、乙酸、丙烯酸及丙酸。Stream (F11) may contain components other than methacrolein. As such a component, for example, methacrylic acid, acrolein, acetone, acetaldehyde, propionaldehyde, terephthalic acid, maleic acid, fumaric acid, diacetyl, isophthalic acid, Isobutyric acid, methyl furfural, acetic acid, acrylic acid and propionic acid.
第一反應器10之出口處之流(F11)之溫度通常為250~400℃,較佳為255~380℃,更佳為260~360℃,進而較佳為265~350℃。The temperature of the flow (F11) at the outlet of the
就甲基丙烯醛及/或甲基丙烯酸之選擇率之觀點而言,第一反應器10之觸媒填充層之出口處之氣體溫度與向第一反應器10之混合氣體之供給溫度之差(觸媒填充層出口溫度-混合氣體供給溫度)較佳為120℃以上,更佳為130℃以上,進而較佳為140℃以上。觸媒填充層出口溫度與混合氣體供給溫度之差例如可設為300℃以下。觸媒填充層出口之氣體溫度例如可藉由熱媒之溫度進行調整。流出觸媒填充層之流在自第一反應器10排出前亦可藉由冷卻區域冷卻。From the viewpoint of the selectivity of methacrolein and/or methacrylic acid, the difference between the gas temperature at the outlet of the catalyst packed layer of the
又,於第一反應器10具備觸媒填充層、及向第一反應器10供給熱媒而調整觸媒填充層之溫度之溫度調整機構之情形時,就甲基丙烯醛及/或甲基丙烯酸之選擇率之觀點而言,供給至第一反應器10之熱媒之溫度與供給至第一反應器10之混合氣體之溫度之差(熱媒溫度-混合氣體供給溫度)較佳為120℃以上,更佳為130℃以上,進而較佳為140℃以上。熱媒溫度與混合氣體供給溫度之差例如可設為300℃以下。Furthermore, when the
第一反應器10中之反應壓力通常為0.004~0.6 MPaG(表壓),較佳為0.006~0.5 MPaG,更佳為0.008~0.4 MPaG,進而較佳為0.01~0.3 MPaG。The reaction pressure in the
對於自第一反應器10排出之流(F11),經由管線L23混合包含甲基丙烯醛之循環流(F23)後,經由管線L22混合含氧氣體之流(F22)。然後,經由管線L21將所獲得之流(F21)供給至第二反應器20。流(F22)所使用之含氧氣體之供給源例如可為流(F0)之供給源。For the stream (F11) discharged from the
於第二反應器20中,自流(F21)中之甲基丙烯醛生成甲基丙烯酸,且經由管線L30排出包含甲基丙烯酸之流(F30)。In the
流(F30)包含未反應之甲基丙烯醛。流(F30)可包含除甲基丙烯酸及甲基丙烯醛以外之成分。作為此種成分,例如可列舉:丙烯酸、丙烯醛、一氧化碳、乙醛、丙醛、對苯二甲酸、順丁烯二酸、反丁烯二酸、雙乙醯、間苯二甲酸、異丁酸、甲基糠醛、乙酸及丙酸。Stream (F30) contains unreacted methacrolein. Stream (F30) may contain ingredients other than methacrylic acid and methacrolein. Examples of such components include acrylic acid, acrolein, carbon monoxide, acetaldehyde, propionaldehyde, terephthalic acid, maleic acid, fumaric acid, diacetate, isophthalic acid, and isobutylene. acid, methyl furfural, acetic acid and propionic acid.
流(F21)之向第二反應器20之供給溫度例如為200~350℃。又,第二反應器20之出口處之流(F30)之溫度例如為250~350℃。第二反應器20中之反應壓力例如為0.01~0.3 MPaG。The supply temperature of the flow (F21) to the
(分離步驟及循環步驟)
流出第二反應器20之流(F30)經由管線L30供給至分離機構60。於分離機構60中,藉由管線L35自上部抽出包含一氧化碳、輕質成分及氧之流(F35),藉由管線L31自下部抽出包含甲基丙烯酸及重質成分之流(F31),藉由管線L23自側面抽出包含甲基丙烯醛之流(F23)。(Separation step and circulation step)
The flow (F30) flowing out of the
流(F35)供給至氣體燃燒機構80。於氣體燃燒機構80中,藉由流中之氧使流(F35)中之一氧化碳及輕質成分燃燒,從而將該等轉換為二氧化碳。燃燒後之流(F38)藉由L38抽出後,藉由溫度調整機構52進行溫度調整。經溫度調整之流作為燃燒氣體(稀釋氣體)之流(F3)通過管線L3循環。The flow ( F35 ) is supplied to the
又,包含甲基丙烯醛之流(F23)經由管線L23循環至L21。Also, the stream (F23) containing methacrolein is recycled to L21 via line L23.
本實施形態之製造方法包括:將含氧氣體與包含異丁烯及第三丁醇中之至少一者之氣體加以混合而獲得混合氣體之步驟(混合步驟)、及將上述混合氣體於100~200℃之溫度下供給至具備氧化觸媒之反應器之步驟(供給步驟)。The production method of the present embodiment includes: a step (mixing step) of obtaining a mixed gas by mixing an oxygen-containing gas with a gas containing at least one of isobutylene and tertiary butanol, and heating the mixed gas at 100 to 200° C. The step of supplying it to a reactor equipped with an oxidation catalyst at the temperature (supplying step).
第一反應器10中之反應溫度通常為350℃左右。就使第一反應器10內之溫度高效率地上升至反應溫度之觀點而言,考慮到混合氣體之向第一反應器10之供給溫度例如設為350℃左右。然而,於此種方法中,甲基丙烯醛及/或甲基丙烯酸之選擇率不充分。另一方面,根據本實施形態之製造方法,可以優異之選擇率製造甲基丙烯醛及/或甲基丙烯酸。The reaction temperature in the
第一反應器10內之反應為放熱反應。就減少反應器內之溫度不均之觀點而言,考慮到減小觸媒填充層之出口之氣體溫度與向第一反應器10之混合氣體之供給溫度之差(觸媒填充層出口溫度-混合氣體供給溫度)。於該情形時,考慮到於接近觸媒填充層出口溫度之溫度下供給混合氣體,且藉由熱媒調整上述填充層之溫度。然而,如上所述,觸媒填充層出口溫度與混合氣體供給溫度之差較佳為120℃以上。又,填充層之進行溫度調整之熱媒之溫度與混合氣體供給溫度之差較佳為120℃以上。藉此,甲基丙烯醛及/或甲基丙烯酸之選擇率進一步提高。The reaction in the
本發明不限於上述實施形態,可為各種變化態樣。The present invention is not limited to the above-described embodiment, and various modifications are possible.
例如,亦可於各管線進一步追加蒸餾塔、抽出塔等分離精製機構。分離機構60亦可為抽出塔或蒸餾塔與抽出塔之組合。For example, separation and purification mechanisms such as a distillation column and an extraction column may be further added to each line. The
又,於上述實施形態中,藉由水蒸氣及溫度調整機構52調整混合氣體之供給溫度,但亦可於氣體混合機50a與第一反應器10之間設置熱交換器等溫度調整機構代替該等。In the above-described embodiment, the supply temperature of the mixed gas is adjusted by the steam and the
管線L3及管線L4可有可無,可為任一者。即,稀釋氣體為燃燒氣體及水蒸氣中之任一者,亦可省略藉由稀釋氣體進行稀釋之步驟。又,燃燒氣體之流(F3)及水蒸氣之流(F4)之供給順序亦可相反。亦可另外設置稀釋氣體之供給管線代替管線L3及管線L4。 [實施例]The line L3 and the line L4 may be present or not, and may be either. That is, the dilution gas may be any one of combustion gas and water vapor, and the step of diluting with the dilution gas may be omitted. In addition, the supply order of the flow of combustion gas (F3) and the flow of water vapor (F4) may be reversed. Instead of the pipeline L3 and the pipeline L4, a supply pipeline of the diluent gas may be additionally provided. [Example]
以下,列舉實施例對本發明進一步具體地進行說明。但,本發明並不限定於該等實施例。Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these Examples.
(氧化觸媒之製備) 藉由下述步驟1~4,調整觸媒Ia。(Preparation of Oxidation Catalyst) The catalyst Ia is adjusted by the following steps 1 to 4.
[步驟1]焙燒體之製備 使鉬酸銨[(NH4 )6 Mo7 O24 ・4H2 O]13241 g溶解於溫水15000 g中,從而獲得A液。[Step 1] Preparation of calcined body A liquid was obtained by dissolving 13,241 g of ammonium molybdate [(NH 4 ) 6 Mo 7 O 24 ·4H 2 O] in 15,000 g of warm water.
於使硝酸鐵(III)[Fe(NO3 )3 ・9H2 O]6060 g、硝酸鈷[Co(NO3 )2 ・6H2 O]13096 g及硝酸銫[CsNO3 ]585 g溶解於溫水6000 g中所獲得之溶液中進一步使硝酸鉍[Bi(NO3 )3 ・5H2 O]2910 g溶解,從而獲得B液。6060 g of iron(III) nitrate [Fe(NO 3 ) 3・9H 2 O], 13096 g of cobalt nitrate [Co(NO 3 ) 2・6H 2 O], and 585 g of cesium nitrate [CsNO 3 ] were dissolved in the temperature. In the solution obtained in 6000 g of water, 2910 g of bismuth nitrate [Bi(NO 3 ) 3 ·5H 2 O] was further dissolved to obtain B liquid.
藉由一面攪拌A液,一面於A液中添加B液而獲得漿料。藉由氣流乾燥機乾燥所獲得之漿料,從而獲得乾燥物。將獲得之乾燥物100質量份與9質量份之矽鋁纖維(Saint-Gobain TM製造,商品名RFC400-SL)及2.5質量份之三氧化二銻(Sb2 O3 )之混合物成型為外徑6.3 mm、內徑2.5 mm、長度6 mm之環狀後,於空氣氣流下於545℃下焙燒6小時。A slurry was obtained by adding liquid B to liquid A while stirring liquid A. The obtained slurry was dried by an air flow dryer to obtain a dried product. A mixture of 100 parts by mass of the obtained dried product, 9 parts by mass of silica-alumina fibers (manufactured by Saint-Gobain TM, trade name RFC400-SL) and 2.5 parts by mass of antimony trioxide (Sb 2 O 3 ) was formed into an outer diameter. After a ring of 6.3 mm, inner diameter of 2.5 mm, and length of 6 mm, it was calcined at 545° C. for 6 hours under an air flow.
經焙燒所獲得之焙燒體相對於鉬12原子包含鉍0.96原子、鐵2.4原子、鈷7.2原子、銫0.48原子、銻0.48原子。The calcined body obtained by calcination contained 0.96 atoms of bismuth, 2.4 atoms of iron, 7.2 atoms of cobalt, 0.48 atoms of cesium, and 0.48 atoms of antimony with respect to 12 atoms of molybdenum.
[步驟2]還原處理 將步驟1所獲得之焙燒體75 mL填充於玻璃管後,以300 mL/分鐘之流量供給氫/氮=5/95(體積比)之混合氣體,於345℃下進行還原處理8小時。繼而,停止氫之供給,於氮氣流下冷卻至室溫,從而獲得還原體。[Step 2] Restoration processing After filling 75 mL of the calcined body obtained in step 1 in a glass tube, a mixed gas of hydrogen/nitrogen=5/95 (volume ratio) was supplied at a flow rate of 300 mL/min, and reduction treatment was performed at 345° C. for 8 hours. Then, the supply of hydrogen was stopped, and it was cooled to room temperature under nitrogen flow, and a reduced body was obtained.
[步驟3]第二段焙燒 將步驟2所獲得之還原體於空氣氣流下於350℃下焙燒3小時,從而獲得觸媒Ia。[Step 3] Second stage roasting The reduced body obtained in step 2 was calcined at 350° C. for 3 hours under an air flow to obtain catalyst Ia.
(實施例1) 作為含氧氣體,準備包含氧14.9體積%及氮85.1體積%之氣體。作為原料氣體,準備包含異丁烯99.5體積%之氣體(TBA之濃度:0體積%,異丁烯及TBA之合計濃度:99.5體積%)。又,準備水蒸氣。繼而,以87體積份、6體積份及7體積份之比率混合含氧氣體、原料氣體及水蒸氣,從而獲得混合氣體。混合氣體之組成為異丁烯6體積%、氧13體積%、水7體積%及氮74體積%。(Example 1) As the oxygen-containing gas, a gas containing 14.9% by volume of oxygen and 85.1% by volume of nitrogen was prepared. As a raw material gas, a gas containing 99.5 vol % of isobutene was prepared (concentration of TBA: 0 vol %, total concentration of isobutene and TBA: 99.5 vol %). Again, prepare water vapor. Next, the oxygen-containing gas, the raw material gas, and the water vapor were mixed at the ratios of 87 parts by volume, 6 parts by volume, and 7 parts by volume, thereby obtaining a mixed gas. The composition of the mixed gas was 6% by volume of isobutene, 13% by volume of oxygen, 7% by volume of water, and 74% by volume of nitrogen.
準備具有觸媒填充層之管型反應器。於觸媒填充層填充有作為氧化觸媒之觸媒Ia 20 g。Prepare a tubular reactor with a catalyst-packed layer. The catalyst filling layer was filled with 20 g of catalyst Ia as an oxidation catalyst.
將所獲得之混合氣體於140℃(流量:87.6 NmL/分鐘)下供給至反應器。觸媒填充層之溫度藉由熱媒調整。具體而言,將反應器之觸媒填充層之出口處之流之溫度以成為350℃之方式進行調整。供給至反應器之熱媒之溫度為350℃。The obtained mixed gas was supplied to the reactor at 140°C (flow rate: 87.6 NmL/min). The temperature of the catalyst filling layer is adjusted by a heat medium. Specifically, the temperature of the flow at the outlet of the catalyst packed layer of the reactor was adjusted so as to be 350°C. The temperature of the heat medium supplied to the reactor was 350°C.
根據下述之方法,算出異丁烯轉化率及選擇率(MACR+MAA)。 (異丁烯之轉化率) 異丁烯之轉化率(%)根據式:[(供給異丁烯之莫耳數)-(未反應異丁烯之莫耳數)]/(供給異丁烯之莫耳數)×100算出。 (選擇率(MACR+MAA)) 甲基丙烯醛(以下稱為MACR)之產率(%)根據式:[(生成之MACR之莫耳數)/(供給異丁烯之莫耳數)]×100算出,MACR之選擇率根據式:(MACR之產率)/(異丁烯之轉化率)×100算出。 甲基丙烯酸(以下稱為MAA)之產率(%)根據式:[(生成之MAA之莫耳數)/(供給異丁烯之莫耳數)]×100算出,MAA之選擇率根據式:(MAA之產率)/(異丁烯之轉化率)×100算出。 選擇率(MACR+MAA)根據式:(MACR之選擇率)+(MAA之選擇率)算出。The isobutene conversion and selectivity (MACR+MAA) were calculated according to the following method. (Conversion rate of isobutylene) The conversion rate (%) of isobutene was calculated according to the formula: [(moles of supplied isobutene)−(moles of unreacted isobutene)]/(moles of supplied isobutene)×100. (Selectivity (MACR+MAA)) The yield (%) of methacrolein (hereinafter referred to as MACR) is calculated according to the formula: [(moles of generated MACR)/(moles of supplied isobutene)]×100, and the selectivity of MACR is calculated according to the formula: (Production rate of MACR)/(Conversion rate of isobutene)×100 was calculated. The yield (%) of methacrylic acid (hereinafter referred to as MAA) was calculated according to the formula: [(moles of MAA produced)/(moles of isobutylene supplied)]×100, and the selectivity of MAA was calculated according to the formula: ( The yield of MAA)/(conversion rate of isobutene)×100 was calculated. The selectivity (MACR+MAA) is calculated according to the formula: (selectivity of MACR)+(selectivity of MAA).
異丁烯轉化率為95.71%,選擇率(MACR+MAA)為76.96%。The conversion rate of isobutene was 95.71%, and the selectivity (MACR+MAA) was 76.96%.
(實施例2) 將混合氣體之向反應器之供給溫度變更為170℃,除此以外,以與實施例1相同之方式進行反應,算出異丁烯轉化率及選擇率(MACR+MAA)。異丁烯轉化率為98.77%,選擇率(MACR+MAA)為74.27%。(Example 2) The reaction was carried out in the same manner as in Example 1, except that the supply temperature of the mixed gas to the reactor was changed to 170°C, and the isobutene conversion and selectivity (MACR+MAA) were calculated. The conversion rate of isobutene was 98.77%, and the selectivity (MACR+MAA) was 74.27%.
(比較例1) 將混合氣體之向反應器之供給溫度變更為224℃,除此以外,以與實施例1相同之方式進行反應,算出異丁烯轉化率及選擇率(MACR+MAA)。異丁烯轉化率為99.43%,選擇率(MACR+MAA)為70.83%。(Comparative Example 1) The reaction was carried out in the same manner as in Example 1, except that the supply temperature of the mixed gas to the reactor was changed to 224°C, and the isobutene conversion and selectivity (MACR+MAA) were calculated. The conversion rate of isobutene was 99.43%, and the selectivity (MACR+MAA) was 70.83%.
(比較例2) 將混合氣體之向反應器之供給溫度變更為252℃,除此以外,以與實施例1相同之方式進行反應,算出異丁烯轉化率及選擇率(MACR+MAA)。異丁烯轉化率為99.43%,選擇率(MACR+MAA)為70.88%。(Comparative Example 2) The reaction was carried out in the same manner as in Example 1, except that the supply temperature of the mixed gas to the reactor was changed to 252°C, and the isobutene conversion and selectivity (MACR+MAA) were calculated. The conversion rate of isobutene was 99.43%, and the selectivity (MACR+MAA) was 70.88%.
將混合氣體之向反應器之供給溫度及選擇率(MACR+MAA)之彙總示於表1。Table 1 summarizes the supply temperature and selectivity (MACR+MAA) of the mixed gas to the reactor.
[表1]
如上所示,可確認根據本發明之方法,可以優異之選擇率製造甲基丙烯醛及/或甲基丙烯酸。As described above, according to the method of the present invention, it was confirmed that methacrolein and/or methacrylic acid can be produced with excellent selectivity.
10:第一反應器 20:第二反應器 50a:氣體混合機 50b:氣體混合機 52:溫度調整機構 55:壓縮機 60:分離機構 80:氣體燃燒機構 100:甲基丙烯醛及/或甲基丙烯酸之製造裝置 F0:含氧氣體之流 F1:包含氧及燃燒氣體之流 F2:原料氣體之流 F3:燃燒氣體之流 F4:水蒸氣之流 F10:混合氣體之流 F11:包含甲基丙烯醛之流 F21:流 F22:含氧氣體之流 F23:包含甲基丙烯醛之流 F30:包含甲基丙烯酸之流 F31:包含甲基丙烯酸及重質成分之流 F35:包含一氧化碳、輕質成分及氧之流 F38:燃燒後之流 L1:管線 L2:管線 L3:管線 L4:管線 L10:管線 L21:管線 L22:管線 L23:管線 L30:管線 L31:管線 L35:管線 L38:管線 L101:管線 L102:管線 L103:管線 L104:管線10: The first reactor 20: Second Reactor 50a: Gas mixer 50b: Gas mixer 52: Temperature adjustment mechanism 55: Compressor 60: Separation mechanism 80: Gas combustion mechanism 100: Production equipment for methacrolein and/or methacrylic acid F0: flow of oxygen-containing gas F1: Flow containing oxygen and combustion gases F2: Stream of raw material gas F3: Flow of combustion gas F4: Stream of water vapor F10: Flow of mixed gas F11: Streams containing methacrolein F21: Stream F22: Flow of oxygen-containing gas F23: Streams containing methacrolein F30: Contains methacrylic acid and the like F31: Streams containing methacrylic acid and heavy components F35: Contains carbon monoxide, light components and oxygen streams F38: Stream after burning L1: pipeline L2: Pipeline L3: Pipeline L4: Pipeline L10: Pipeline L21: Pipeline L22: Pipeline L23: Pipeline L30: Pipeline L31: Pipeline L35: Pipeline L38: Pipeline L101: Pipeline L102: Pipeline L103: Pipeline L104: Pipeline
圖1係表示本發明之一實施形態之甲基丙烯醛及/或甲基丙烯酸之製造方法的流程圖。Fig. 1 is a flow chart showing a method for producing methacrolein and/or methacrylic acid according to an embodiment of the present invention.
10:第一反應器 10: The first reactor
20:第二反應器 20: Second Reactor
50a:氣體混合機 50a: Gas mixer
50b:氣體混合機 50b: Gas mixer
52:溫度調整機構 52: Temperature adjustment mechanism
55:壓縮機 55: Compressor
60:分離機構 60: Separation mechanism
80:氣體燃燒機構 80: Gas combustion mechanism
100:甲基丙烯醛及/或甲基丙烯酸之製造裝置 100: Production equipment for methacrolein and/or methacrylic acid
F0:含氧氣體之流 F0: flow of oxygen-containing gas
F1:包含氧及燃燒氣體之流 F1: Flow containing oxygen and combustion gases
F2:原料氣體之流 F2: Stream of raw material gas
F3:燃燒氣體之流 F3: Flow of combustion gas
F4:水蒸氣之流 F4: Stream of water vapor
F10:混合氣體之流 F10: Flow of mixed gas
F11:包含甲基丙烯醛之流 F11: Streams containing methacrolein
F21:流 F21: Stream
F22:含氧氣體之流 F22: Flow of oxygen-containing gas
F23:包含甲基丙烯醛之流 F23: Streams containing methacrolein
F30:包含甲基丙烯酸之流 F30: Contains methacrylic acid and the like
F31:包含甲基丙烯酸及重質成分之流 F31: Streams containing methacrylic acid and heavy components
F35:包含一氧化碳、輕質成分及氧之流 F35: Contains carbon monoxide, light components and oxygen streams
F38:燃燒後之流 F38: Stream after burning
L1:管線 L1: pipeline
L2:管線 L2: Pipeline
L3:管線 L3: Pipeline
L4:管線 L4: Pipeline
L10:管線 L10: Pipeline
L21:管線 L21: Pipeline
L22:管線 L22: Pipeline
L23:管線 L23: Pipeline
L30:管線 L30: Pipeline
L31:管線 L31: Pipeline
L35:管線 L35: Pipeline
L38:管線 L38: Pipeline
L101:管線 L101: Pipeline
L102:管線 L102: Pipeline
L103:管線 L103: Pipeline
L104:管線 L104: Pipeline
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