JP2004097891A - Manufacturing method of catalyst for converting lower hydrocarbon to aromatic compound, catalyst and conversion method for lower hydrocarbon - Google Patents
Manufacturing method of catalyst for converting lower hydrocarbon to aromatic compound, catalyst and conversion method for lower hydrocarbon Download PDFInfo
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- JP2004097891A JP2004097891A JP2002260706A JP2002260706A JP2004097891A JP 2004097891 A JP2004097891 A JP 2004097891A JP 2002260706 A JP2002260706 A JP 2002260706A JP 2002260706 A JP2002260706 A JP 2002260706A JP 2004097891 A JP2004097891 A JP 2004097891A
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- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、低級炭化水素の芳香族化合物化触媒の製造方法と低級炭化水素の芳香族化合物化触媒および低級炭化水素の転化方法であって、例えば天然ガス等の低級炭化水素から化学工業、薬品類、プラスチック類などの化学製品の原料であるベンゼンおよびナフタレン類を主成分とする芳香族化合物と高純度の水素ガスを効率的に製造する際に有効なものである。
【０００２】
【従来の技術】
ベンゼン，トルエン，キシレン等の芳香族化合物は主にナフサを用いて製造されるが、その芳香族化合物と共に水素ガスも製造される。前記の芳香族化合物，水素ガスの製造方法については、以下に示すものが挙げられる。
【０００３】
［非触媒方法によるナフタレン類の製造方法］
ナフタレン類の製造方法として、例えば石炭等を原料とした溶剤抽出法，天然ガスやアセチレンガス等を原料とした熱分解法（ガス分解法）等の非触媒方法が知られていた。しかし、前記の各製造方法の場合、石炭やアセチレンなどの原料から抽出（転化）されるベンゼンおよびナフタレン類は僅か（原料に対して数パーセント）であり、副生芳香族化合物，炭化水素，タール，非溶解性の炭素残留物が多量に生成されてしまう問題がある。
【０００４】
また、前記の石炭等を原料とした溶媒抽出法は多量の有機溶媒を必要とするため、製造コストが高くなってしまう。前記のアセチレン等を原料とした熱分解法においては、例えば数パーセント以上の転化率にてナフタレン類を製造しようとする場合には反応温度を１０００℃以上の高温に設定する必要があると共に、抽出されるナフタレン類は極めて僅か（数パーセント以下）であるため、実用上問題があった。
【０００５】
［触媒を用いたナフタレン類の製造方法］
触媒を用いたナフタレン類の製造方法として、例えば白金類が担持されて成る触媒を介し、オルトオキシレン等のアルキルベンゼン類を高温雰囲気下で脱水素縮合化反応させて製造する方法が知られていたが、そのアルキルベンゼン類が高価であると共に、アルキルベンゼン類からナフタレン類への転化率は低いため、実用上問題があった。
【０００６】
［水素ガスの製造方法］
前記の芳香族化合物と共に併産される水素ガスの製造方法として、高温・高圧雰囲気下にて水成ガス反応（ウォーターガスシフト）および天然ガスの水蒸気改質反応を利用した方法や、原油を原料とした熱分解法等が知られていた。しかし、前記の方法によって製造された水素ガス中には、触媒毒である硫黄や窒素酸化物等が含まれたり、その水素ガスの副生物である一酸化炭素等が含まれてしまう。このため、前記の水素ガス中から触媒毒を除去するための設備を必要とし、精製工程に多大な負荷がかかってしまい、工業的な問題があった。また、前記の水素ガスの製造に伴って多量の炭酸ガスが副生排出されるため、地球環境上問題があった。
【０００７】
［芳香族化合物と水素ガスとを併産する方法］
低級炭化水素（特に、メタンからベンゼン等の低級炭化水素）から成る芳香族化合物と水素ガスとを同時に製造（併産）する方法としては、触媒を介し無酸素雰囲気下（酸素や酸化剤が存在しない状態）にてメタンを反応させる方法が知られ、前記の触媒としてはＺＳＭ−５（担体）にモリブデンを担持させて成るものが有効であるとされていた（「ＪＯＵＲＮＡＬ ＯＦ ＣＡＴＡＬＹＳＩＳ」１６５頁、１５０−１６１頁（１９９７年）、および該文献に引用された文献等）。しかし、前記のように単にＺＳＭ−５にモリブデン担持させた触媒を介しても、炭素析出が多くメタンから炭素ガスへの転化率が低い問題があった。
【０００８】
以上示した各製造方法の他に、特開平１０−２７２３６６号公報，特開平１１−６０５１４号公報，特開２００１−３３４１５１号公報，特開２００１−３３４１５２号公報では、多孔質のメタロシリケートにモリブデンを担持させて成る触媒を用いる方法が提案され、特に触媒の担体として約５．５オングストロームの細孔径を有する多孔質のメタロシリケートを用いた場合には、低級炭化水素が効率的に芳香族化合物へ転化されると共に、高純度の水素ガスが得られることを開示している。
【０００９】
【非特許文献１】
「ＪＯＵＲＮＡＬ ＯＦ ＣＡＴＡＬＹＳＩＳ」，１９９７年，１６５頁，１５０−１６１頁。
【００１０】
【特許文献１】
特開平１０−２７２３６６号公報（段落［０００８］〜［００１３］，［００１９］）。
【００１１】
【特許文献２】
特開平１１−６０５１４号公報（段落［０００７］〜［００１１］，［００２０］）。
【００１２】
【特許文献３】
特開２００１−３３４１５１号公報（段落［０００７］〜［００１４］）。
【００１３】
【特許文献４】
特開２００１−３３４１５２号公報（段落［０００８］〜［００１１］）。
【００１４】
【発明が解決しようとする課題】
前記のようにモリブデン等の触媒金属を担体に担持させる方法としては、例えば触媒金属が溶解された水溶液中に担体を所定の条件（例えば、含浸時間，温度等）で含浸（含浸方法）させることにより、担体に触媒金属を担持させた後、その担持体を前記水溶液中から取り出し乾燥（余分な水分の除去）した後に焼成処理する方法が知られている。また、担持方法としては前記の含浸方法の他に、イオン交換方法により触媒金属を担体に担持させる方法も知られている。
【００１５】
しかし、前記の方法により製造した触媒においては、触媒能（例えば、芳香族化合物や水素ガスへの転化率）の低下が確認され、これは水溶液中から取り出した担持体を乾燥（例えば、単に温度のみを調整しながら乾燥）した際に、担持体に担持された触媒金属が凝集されているためと考えられる。
【００１６】
本発明は前記課題に基づいてなされたものであり、含浸方法またはイオン交換方法により触媒金属が担持された担持体の乾燥方法を改良し、その触媒能を高め、例えば触媒を介して低級炭化水素から芳香族化合物や水素ガスへ転化する際の効率を向上させる触媒の製造方法および触媒と、その触媒を用いた低級炭化水素の転化方法を提供することにある。
【００１７】
【課題を解決するための手段】
本発明は前記の課題の解決を図るために、請求項１記載の発明は、含浸方法またはイオン交換方法により触媒金属をメタロシリケートから成る担体に担持させて担持体を得、その担持体を乾燥し水分除去してから焼成処理する低級炭化水素の芳香族化合物化触媒の製造方法において、前記担持体の乾燥は、減圧雰囲気下にて行うことを特徴とする。具体的には、例えば減圧乾燥器を用い、４ｋＰａの減圧下において、５０℃で１２時間減圧乾燥して余分な水分を蒸発させて乾燥させる。
【００１８】
請求項２の発明は、含浸方法またはイオン交換方法により触媒金属をメタロシリケートから成る担体に担持させて担持体を得、その担持体を乾燥し水分除去してから焼成処理する低級炭化水素の芳香族化合物化触媒の製造方法において、前記担持体の乾燥は、その乾燥温度を徐々に上昇させると共に、その乾燥温度の上昇度合いに応じて湿度を徐々に降下させながら行うことを特徴とする。具体的には、例えば温湿度調節機能付乾燥器を用い、温度３０℃，相対湿度９０％から１２時間かけて温度１００℃，相対湿度０％へと変化させて余分な水分を蒸発させて乾燥させる。
【００１９】
請求項３の発明は、請求項１又は２の触媒金属として、モリブデン，レニウム，タングステン，鉄，コバルト、ならびにそれらの化合物から選ばれた少なくとも一種から成ることを特徴とする。
【００２０】
請求項４の発明は、低級炭化水素の芳香族化合物化触媒を、請求項１乃至３の何れかに記載の低級炭化水素の芳香族化合物化触媒の製造方法によりを製造したことを特徴とする。
【００２１】
請求項５の発明は、請求項４に記載の触媒の存在下で、低級炭化水素を反応させて芳香族炭化物を主成分とする芳香族化合物と水素とを製造することを特徴とする。
【００２２】
ここで、本発明で使用する担体のメタロシリケート（多孔質メタロシリケート）としては、例えばアルミノシリケートの場合、シリカおよびアルミナから成り多孔質体であるモレキュラーシーブ５Ａ，フォジャサイト（ＮａＹおよびＮａＸ），ＺＳＭ−５，ＭＣＭ−２２が挙げられる。また、リン酸を主成分とする多孔質体でＡＬＰＯ−５，ＶＰＩ−５等の６〜１３オングストロームのミクロ細孔やチャンネルからなることを特徴とするゼオライト担体や、シリカを主成分とし一部アルミナを成分として含むメゾ細孔（１０〜１０００オングストローム）の筒状細孔（チャンネル）で特徴付けられるＦＳＭ−１６やＭＣＭ−４１等のメゾ細孔多孔質担体などが例示できる。さらに、前記アルミナシリケートの他に、シリカおよびチタニアからなるメタロシリケート等も触媒として用いることができる。
【００２３】
また、本発明で使用する担体のメタロシリケートは、表面積が２００〜１０００ｍ２／ｇであり、そのミクロおよびメゾ細孔は５〜１００オングストロームの範囲内のものが望ましい。また、メタロシリケートが例えばアルミノシリケートである場合、そのシリカとアルミナの含有比（シリカ／アルミナ）が通常入手し得る多孔質体と同様にシリカ／アルミナ＝１〜８０００のものを用いることができるが、本発明の低級炭化水素の芳香族化反応を、実用的な低級炭化水素の転化率および芳香族化合物への選択率で実施するためには、シリカ／アルミナ＝１０〜１００の範囲内とすることがより好ましい。
【００２４】
さらに、本発明の触媒金属（を含む前駆体）をメタロシリケートに担持させる場合、触媒金属と担体との重量比は０．００１〜５０％、好ましくは０．０１〜４０％の範囲で行う。また、メタロシリケートへ担持させる方法としては、前述した触媒金属の前駆体の水溶液、あるいはアルコール等の有機溶媒の溶液からメタロシリケート担体に含浸担持あるいはイオン交換方法により担持させた後、不活性ガスあるいは酸素ガス雰囲気下で加熱処理する方法がある。この方法をより具体的に説明すると、まず、例えばメタロシリケート担体にモリブデン酸アンモニウム塩の水溶液を含浸担持させ、その担持体を乾燥して溶媒を除いた後、窒素含有酸素気流中または純酸素気流中にて温度２５０〜８００℃（好ましくは３５０〜６００℃）で加熱処理して、触媒金属を担持したメタロシリケート触媒を製造することができる。
【００２５】
そして、本発明の触媒金属としてはモリブデンを用いることが好ましいが、レニウム，タングステン，鉄，コバルトを用いても良い。触媒金属のうちモリブデンを含む前駆体の例としては、パラモリブデン酸アンモニウム，リンモリブデン酸アンモニウム，１２系モリブデン酸の他に、塩化物，臭化物等のハロゲン化物，硝酸塩，硫酸塩，リン酸塩等の鉱酸塩，炭酸塩，酢酸塩，蓚酸塩等のカルボン酸塩等を挙げることができる。
【００２６】
なお、本発明の低級炭化水素の芳香族化合物化触媒は、粉末状またはペレット状またはハニカムモノリス形状またはリング形状およびその他形状を問わず使用することができ、メタロシリケートを前記の形状に加工するために、例えば粘土などの無機バインダーをメタロシリケートに対して１〜２０重量％の範囲で用いても良い。
【００２７】
【発明の実施の形態】
以下、本発明の実施の形態における低級炭化水素の芳香族化合物化触媒（以下、「触媒」と省略する。）の製造方法および低級炭化水素の転化方法を図面等に基づいて詳細に説明する。
【００２８】
本実施の形態における触媒の製造方法において、まずモリブデン等の触媒金属が溶解された水溶液中に対し、例えば多孔質メタロシリケート等の担体を所定時間含浸させることにより、前記の触媒金属を担体に担持させて担持体を得る。その後、前記の担持体を水溶液中から取り出し、減圧雰囲気下にて所定温度で乾燥（以下、減圧乾燥と称する）することにより水分を除去し、その担体を加熱処理（焼成）して触媒を作製する。
【００２９】
または、前記のように触媒金属が担持され水溶液中から取り出された担持体を、乾燥温度を徐々に上昇（例えば、室温から温度１２０℃の範囲内で徐々に上昇）させると共に乾燥温度の上昇度合いに応じて相対湿度を徐々に降下（例えば、相対湿度９０％以上から０％の範囲内で徐々に降下）させながら乾燥（以下、調湿度乾燥と称する）することにより水分を除去し、加熱処理（焼成）して触媒を作製する。
【００３０】
そして、前記の方法で製造した触媒の存在下にて低級炭化水素を反応させたところ、触媒能が低下することなく、芳香族化合物や水素ガスを製造することができた。
【００３１】
これは、本実施の形態のように触媒金属が担持された担持体を減圧乾燥または調湿度乾燥したことにより、担持体の水分が徐々に蒸発して除去されることで、担持体に担持された触媒金属の凝集が防止されたと考えることができ、これにより触媒能の高い触媒が得られたものと思われる。また、前記の方法により製造した触媒を用いることにより、低級炭化水素から芳香族化合物，水素ガスへの転化率が向上するため、それら芳香族化合物，水素ガスを効率良く製造することができた。
【００３２】
［実施例］
次に、本実施の形態における触媒の製造方法により種々の触媒の試料を作製し、それら試料を用いた場合の低級炭化水素（本実施例ではメタン）から芳香族化合物（本実施例ではベンゼン），水素ガスへの転化率を調べた。なお、本実施例における「メタン転化率」，「炭化水素選択率」，「炭化水素の分布」，「水素生成速度」は、以下に示すように定義した。
【００３３】
・「メタン転化率（％）」＝〔（「原料メタン流速」−「未反応のメタン流速」）／「原料メタン流速」〕×１００
・「炭化水素選択率（％）」＝〔「生成した全炭化水素のメタン換算流速」／（「原料メタン流速」−「未反応のメタン流速」）〕×１００
・「炭化水素の分布（％）」＝（「着目する炭化水素のメタン換算流速」／「生成した全炭化水素のメタン換算流速」）×１００
・「水素ガス生成速度」＝「触媒１ｇあたり、１秒間に生成した水素のｎｍｏｌ数」
・「ベンゼン生成速度」＝「触媒１ｇあたり、１秒間に生成したベンゼンのｎｍｏｌ数」。
【００３４】
まず、触媒金属の前駆体として７モリブデン酸アンモニウム塩を４５６．５ｇ用い、その前駆体を２０００ｍｌの蒸留水に溶解して水溶液を得た。また、メタロシリケートであるＨＺＳＭ−５（シリカ／アルミナ比＝４０）と無機成形バインダーとを重量比８０：２０の割合で混合し、その混合物により壁厚さ０．８ｍｍで７０セル／インチの正方形セル形状を有する直径１．８ｃｍ，長さ１０ｃｍの円筒形ハニカム成形体（重量１３ｇ）を２６本（全ハニカム成形体重量３３８ｇ）を作製した。
【００３５】
そして、前記２６本のハニカム成形体を、前記水溶液中に３時間含浸させることにより、触媒金属を担持させた担持体を得た。
【００３６】
次に、これら２６本の担持体のうち８本を、減圧乾燥機により４ｋＰａの減圧雰囲気下にて温度５０℃で１２時間減圧乾燥させて余分な水分を蒸発除去した後、バッチ式焼成炉を用いて、前記の担持体を大気条件下にて温度５００℃で４時間焼成することにより、薄黄色の円筒形ハニカム成形体から成りモリブデンが担持された触媒（ＨＺＳＭ−５の重量比が触媒全体に対して６．８ｗｔ％の触媒）の試料Ｓ１を作製した。
【００３７】
また、前記担持体２６本のうち９本を、温度・湿度調整機能付き乾燥機を用いて乾燥温度を３０℃〜１００℃の範囲内で１２時間費やして徐々に上昇させると共に、その乾燥温度の上昇度合いに応じて湿度を９０％〜０％の範囲内で徐々に降下させながら調湿度乾燥した後、試料Ｓ１と同様の方法で焼成することにより、薄黄色の円筒形ハニカム成形体から成りモリブデンが担持された触媒（ＨＺＳＭ−５の重量比が触媒全体に対して６．８ｗｔ％の触媒）の試料Ｓ２を作製した。
【００３８】
更に、前記担持体２６本のうち残りの９本については、温度調整機能付き乾燥器を用い、乾燥温度を３０℃から１００℃へ、１２時間費やして徐々に上昇させながら乾燥した後、試料Ｓ１と同様の方法により焼成することにより、薄黄色の円筒形ハニカム成形体から成りモリブデンが担持された触媒（ＨＺＳＭ−５の重量比が触媒全体に対して６．８ｗｔ％の触媒）の試料Ｐを作製した。
【００３９】
前記のように作製した試料Ｓ１，Ｓ２，Ｐについて、固定床流通式反応装置のインコネル８００Ｈ接ガス部カロライジング処理製反応管（内径１８ｍｍ）内にそれぞれ充填し、その反応管内の反応温度を７５０℃，圧力を０．３ＭＰａに設定すると共に、メタン反応ガスを空間速度３０００ｍｌ／ｈｒ／ｇ−ＭＦＩの流量で供給することにより、メタンの芳香族化反応によるベンゼンおよび水素ガスの生成反応活性をそれぞれ調べた。その反応開始から３００分経過後の各生成速度を下記表１に示した。また、前記ベンゼンの反応開始から６００時間までの各生成速度については、図１の反応経過時間に対する生成速度特性図に示した。
【００４０】
【表１】
前記表１および図１に示すように、試料Ｓ１，Ｓ２を用いた場合のベンゼン生成速度，水素ガス生成速度は、それぞれ試料Ｐに比べて大きいことが読み取れ、特に試料Ｓ２を用いた場合に優れた結果が得られた。
【００４２】
ゆえに、本実施例のように、モリブデン等の触媒金属が担持された担持体を減圧乾燥または調湿度乾燥して余分な水分を蒸発除去することにより、前記触媒金属の凝集を抑制し触媒能の高い触媒が得られることを確認できた。また、前記の触媒を用いることにより、メタン等の低級炭化水素を高い生成速度でベンゼン等の芳香族化合物や水素ガスに転化できることを確認できた。
【００４３】
以上、本発明において、記載された具体例に対してのみ詳細に説明したが、本発明の技術思想の範囲で多彩な変形および修正が可能であることは、当業者にとって明白なことであり、このような変形および修正が特許請求の範囲に属することは当然のことである。
【００４４】
例えば、本実施例においては触媒金属としてモリブデンを用いているが、既に低級炭化水素の芳香族化合物化触媒としての効果が確認され、文献（例えば、『表面』ｖｏｌ．３７Ｎｏ．１２（１９９９）７１頁〜８１頁「メタンの触媒化学的変換−鋳型ゼオライト触媒を用いるベンゼン直接合成」）等で紹介されている各種触媒金属のうち、レニウム，タングステン，鉄，コバルト、ならびにそれら（モリブデンを含む）の化合物を単独又は組み合わせて用いた場合においても、同様の作用効果が得られることを確認することができた。
【００４５】
また、本実施例では含浸方法により触媒金属が担持された担持体の乾燥方法についてのみ示したが、イオン交換方法により触媒金属が担持された担持体に適用した場合においても、同様の作用効果が得られることを確認した。
【００４６】
さらに、本実施例では、ハニカム形状の担体を用いたが、粉末状，ペレット状，リング形状の担体を用いた場合においても、同様の作用効果が得られることを確認した。
【００４７】
【発明の効果】
以上示したように本発明によれば、触媒金属が担持された担持体を減圧乾燥または調湿度乾燥することにより、担持体の水分が徐々に蒸発して除去され、担持体に担持された触媒金属の凝集を防ぐことができると考えられ、結果、触媒能の高い触媒が得ることができる。また、前記の触媒を用いることにより、例えば低級炭化水素から芳香族化合物，水素ガスへの転化率が向上するため、天然ガス等の低級炭化水素から化学工業、薬品類、プラスチック類などの化学製品の原料であるベンゼンおよびナフタレン類を主成分とする芳香族化合物と高純度の水素ガスを効率的に製造することが可能となる。
【図面の簡単な説明】
【図１】本実施例における各試料の反応経過時間に対する生成速度特性図。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a lower hydrocarbon aromatic compound conversion catalyst, a lower hydrocarbon aromatic compound conversion catalyst and a lower hydrocarbon conversion method, for example, from lower hydrocarbons such as natural gas to chemical industry, chemicals, and the like. It is effective in efficiently producing aromatic compounds containing benzene and naphthalenes as the main components and high-purity hydrogen gas, which are raw materials of chemical products such as alcohols and plastics.
[0002]
[Prior art]
Aromatic compounds such as benzene, toluene, and xylene are mainly produced using naphtha, and hydrogen gas is produced together with the aromatic compounds. The method for producing the aromatic compound and hydrogen gas includes the following.
[0003]
[Production method of naphthalenes by non-catalytic method]
As a method for producing naphthalenes, for example, non-catalytic methods such as a solvent extraction method using coal or the like as a raw material and a thermal decomposition method (gas decomposition method) using natural gas or acetylene gas as a raw material have been known. However, in each of the above-mentioned production methods, benzene and naphthalenes extracted (converted) from raw materials such as coal and acetylene are small (several percent with respect to the raw materials), and aromatic by-products, hydrocarbons and tar In addition, there is a problem that a large amount of insoluble carbon residue is generated.
[0004]
Further, the above-mentioned solvent extraction method using coal or the like as a raw material requires a large amount of an organic solvent, which increases the production cost. In the above-mentioned pyrolysis method using acetylene or the like as a raw material, for example, when it is desired to produce naphthalenes at a conversion of several percent or more, it is necessary to set the reaction temperature to a high temperature of 1000 ° C. or more, and to perform extraction. Since the amount of naphthalenes produced is extremely small (several percent or less), there is a practical problem.
[0005]
[Method for producing naphthalenes using catalyst]
As a method for producing naphthalenes using a catalyst, for example, a method has been known in which an alkylbenzene such as orthooxylene is subjected to a dehydrocondensation reaction under a high-temperature atmosphere through a catalyst on which platinum is supported, for example. However, since the alkylbenzenes are expensive and the conversion ratio of the alkylbenzenes to naphthalenes is low, there is a practical problem.
[0006]
[Method for producing hydrogen gas]
Examples of a method for producing hydrogen gas co-produced with the aromatic compound include a method using a hydrogas reaction (water gas shift) and a steam reforming reaction of natural gas under a high temperature and high pressure atmosphere, and a method using crude oil as a raw material. Thermal decomposition methods and the like have been known. However, the hydrogen gas produced by the above-mentioned method contains sulfur or nitrogen oxides which are catalyst poisons, or carbon monoxide which is a by-product of the hydrogen gas. For this reason, equipment for removing catalyst poisons from the hydrogen gas is required, and a great load is applied to the purification process, which has been an industrial problem. In addition, since a large amount of carbon dioxide is discharged as a by-product of the production of hydrogen gas, there is a problem on the global environment.
[0007]
[Method of co-producing aromatic compound and hydrogen gas]
As a method of simultaneously producing (co-producing) an aromatic compound composed of lower hydrocarbons (particularly lower hydrocarbons such as methane to benzene) and hydrogen gas, a catalyst is used under an oxygen-free atmosphere (in the presence of oxygen or an oxidizing agent). A method in which methane is reacted in a state in which no methane is reacted is known. As the above-mentioned catalyst, a catalyst obtained by supporting molybdenum on ZSM-5 (carrier) has been considered to be effective ("JOURNAL OF CATALYSIS", page 165; 150-161 (1997), and references cited therein. However, even though a catalyst in which molybdenum is supported on ZSM-5 simply as described above, there has been a problem that carbon deposition is large and the conversion from methane to carbon gas is low.
[0008]
In addition to the production methods described above, in JP-A-10-272366, JP-A-11-60514, JP-A-2001-334151 and JP-A-2001-334152, molybdenum is used as a porous metallosilicate. In particular, when a porous metallosilicate having a pore diameter of about 5.5 angstroms is used as a carrier for the catalyst, the lower hydrocarbon can efficiently convert the aromatic compound. And that high-purity hydrogen gas can be obtained.
[0009]
[Non-patent document 1]
"JOURNAL OF CATALYSIS", 1997, 165, 150-161.
[0010]
[Patent Document 1]
JP-A-10-272366 (paragraphs [0008] to [0013], [0019]).
[0011]
[Patent Document 2]
JP-A-11-60514 (paragraphs [0007] to [0011], [0020]).
[0012]
[Patent Document 3]
JP 2001-334151 A (paragraphs [0007] to [0014]).
[0013]
[Patent Document 4]
JP 2001-334152 A (paragraphs [0008] to [0011]).
[0014]
[Problems to be solved by the invention]
As described above, as a method of supporting a catalyst metal such as molybdenum on a carrier, for example, the carrier is impregnated (impregnation method) in an aqueous solution in which the catalyst metal is dissolved under predetermined conditions (eg, impregnation time, temperature, etc.). Thus, a method is known in which after a catalyst metal is supported on a carrier, the support is taken out of the aqueous solution, dried (removal of excess water), and then calcined. As a supporting method, in addition to the above-mentioned impregnation method, a method of supporting a catalytic metal on a carrier by an ion exchange method is also known.
[0015]
However, in the catalyst produced by the above-described method, a decrease in catalytic ability (for example, conversion to an aromatic compound or hydrogen gas) was confirmed. This was because the support taken out of the aqueous solution was dried (for example, simply by temperature It is considered that the catalyst metal supported on the support was agglomerated when the drying was performed while adjusting only the temperature.
[0016]
The present invention has been made based on the above-mentioned problem, and has improved a method of drying a support on which a catalyst metal is supported by an impregnation method or an ion exchange method to enhance its catalytic ability, for example, a lower hydrocarbon through a catalyst. It is an object of the present invention to provide a method for producing a catalyst and a catalyst for improving the efficiency of converting hydrogen into an aromatic compound and hydrogen gas, and a method for converting a lower hydrocarbon using the catalyst.
[0017]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present invention provides a catalyst metal supported on a metallosilicate carrier by an impregnation method or an ion exchange method to obtain a carrier, and the carrier is dried. In the method for producing a catalyst for converting a lower hydrocarbon to an aromatic compound which is subjected to a calcination treatment after removing water, the drying of the support is performed under a reduced-pressure atmosphere. Specifically, for example, using a reduced-pressure drier, the mixture is dried under reduced pressure of 4 kPa at 50 ° C. for 12 hours to evaporate excess moisture and dry.
[0018]
The invention according to
[0019]
The invention of claim 3 is characterized in that the catalyst metal of
[0020]
The invention of claim 4 is characterized in that the lower hydrocarbon aromatic compound conversion catalyst is produced by the method for producing a lower hydrocarbon aromatic compound catalyst according to any one of
[0021]
The invention of claim 5 is characterized in that a lower hydrocarbon is reacted in the presence of the catalyst of claim 4 to produce an aromatic compound mainly composed of an aromatic carbide and hydrogen.
[0022]
Here, as a metallosilicate (porous metallosilicate) as a carrier used in the present invention, for example, in the case of aluminosilicate, molecular sieve 5A which is a porous body composed of silica and alumina, fausite (NaY and NaX), ZSM-5 and MCM-22. Further, a zeolite carrier characterized by being composed of micropores or channels of 6 to 13 Å, such as ALPO-5 and VPI-5, which is a porous body mainly composed of phosphoric acid, Examples include mesoporous porous carriers such as FSM-16 and MCM-41, which are characterized by cylindrical pores (channels) of mesopores (10 to 1000 angstroms) containing alumina as a component. Further, in addition to the alumina silicate, a metallosilicate composed of silica and titania or the like can be used as a catalyst.
[0023]
The metallosilicate used as the carrier in the present invention preferably has a surface area of 200 to 1000 m 2 / g, and has micro and mesopores in the range of 5 to 100 Å. When the metallosilicate is, for example, aluminosilicate, the content ratio of silica to alumina (silica / alumina) can be the same as that of a generally available porous material, but silica / alumina = 1 to 8000 can be used. In order to carry out the aromatization reaction of lower hydrocarbons of the present invention with a practical conversion of lower hydrocarbons and selectivity to aromatic compounds, silica / alumina is in the range of 10 to 100. Is more preferable.
[0024]
Further, when the catalyst metal (including a precursor) of the present invention is supported on a metallosilicate, the weight ratio of the catalyst metal to the carrier is in the range of 0.001 to 50%, preferably 0.01 to 40%. In addition, as a method of supporting on the metallosilicate, an aqueous solution of the above-described catalyst metal precursor, or a solution of an organic solvent such as alcohol is supported on the metallosilicate carrier by impregnation or ion exchange method, and then inert gas or There is a method of performing heat treatment in an oxygen gas atmosphere. This method will be described more specifically. First, for example, an aqueous solution of ammonium molybdate is impregnated and supported on a metallosilicate support, and the support is dried to remove the solvent. Heat treatment at a temperature of 250 to 800 ° C. (preferably 350 to 600 ° C.) can produce a metallosilicate catalyst supporting a catalytic metal.
[0025]
Although molybdenum is preferably used as the catalyst metal of the present invention, rhenium, tungsten, iron, and cobalt may be used. Examples of the precursor containing molybdenum among the catalyst metals include ammonium paramolybdate, ammonium phosphomolybdate, 12-type molybdic acid, halides such as chlorides and bromides, nitrates, sulfates, phosphates and the like. And carboxylate such as carbonate, acetate, oxalate and the like.
[0026]
Note that the lower hydrocarbon aromatic compound conversion catalyst of the present invention can be used in any form of powder, pellet, honeycomb monolith, ring, and other shapes, for processing metallosilicate into the above-described shape. In addition, an inorganic binder such as clay may be used in the range of 1 to 20% by weight based on the metallosilicate.
[0027]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a method for producing a catalyst for converting a lower hydrocarbon into an aromatic compound (hereinafter abbreviated as “catalyst”) and a method for converting a lower hydrocarbon according to an embodiment of the present invention will be described in detail with reference to the drawings and the like.
[0028]
In the method for producing a catalyst according to the present embodiment, first, an aqueous solution in which a catalyst metal such as molybdenum is dissolved is impregnated with a carrier such as a porous metallosilicate for a predetermined time, whereby the catalyst metal is supported on the carrier. Thus, a carrier is obtained. Thereafter, the carrier is taken out of the aqueous solution, dried at a predetermined temperature under reduced pressure atmosphere (hereinafter, referred to as reduced pressure drying) to remove water, and the carrier is heated (baked) to prepare a catalyst. I do.
[0029]
Alternatively, the drying temperature of the carrier, on which the catalyst metal is supported and taken out from the aqueous solution as described above, is gradually increased (for example, gradually from room temperature to a temperature of 120 ° C.) and the drying temperature is increased. The moisture is removed by drying (hereinafter referred to as humidity controlled drying) while gradually lowering the relative humidity (for example, gradually falling within a range of 90% or more of relative humidity to 0%) in accordance with (Calcination) to produce a catalyst.
[0030]
When lower hydrocarbons were reacted in the presence of the catalyst produced by the above-mentioned method, aromatic compounds and hydrogen gas could be produced without lowering the catalytic ability.
[0031]
This is because the carrier on which the catalytic metal is carried as in this embodiment is dried under reduced pressure or controlled humidity, whereby the water on the carrier is gradually evaporated and removed, so that the carrier is supported on the carrier. It can be considered that the aggregation of the catalyst metal was prevented, and it was considered that a catalyst having high catalytic ability was obtained. Further, by using the catalyst produced by the above method, the conversion of lower hydrocarbons to aromatic compounds and hydrogen gas is improved, so that the aromatic compounds and hydrogen gas can be produced efficiently.
[0032]
[Example]
Next, samples of various catalysts were prepared by the method for producing a catalyst according to the present embodiment, and a lower hydrocarbon (methane in the present example) was converted to an aromatic compound (benzene in the present example) using the samples. The conversion rate to hydrogen gas was investigated. The “methane conversion”, “hydrocarbon selectivity”, “hydrocarbon distribution”, and “hydrogen generation rate” in this example were defined as follows.
[0033]
"Methane conversion rate (%)" = [("raw methane flow rate"-"unreacted methane flow rate") / "raw methane flow rate"] x 100
・ “Hydrocarbon selectivity (%)” = [“Methane equivalent flow rate of all generated hydrocarbons” / (“Material methane flow rate” − “Unreacted methane flow rate”)] × 100
・ “Distribution (%) of hydrocarbons” = (“Methane-converted flow rate of hydrocarbon of interest” / “Methane-converted flow rate of all generated hydrocarbons”) × 100
・ “Hydrogen gas generation rate” = “nmol number of hydrogen generated per second per gram of catalyst”
-"Benzen production rate" = "nmol number of benzene produced per second per gram of catalyst".
[0034]
First, 456.5 g of ammonium 7-molybdate was used as a catalyst metal precursor, and the precursor was dissolved in 2000 ml of distilled water to obtain an aqueous solution. Also, a metallosilicate HZSM-5 (silica / alumina ratio = 40) and an inorganic molding binder were mixed at a weight ratio of 80:20, and the mixture was used to form a square of 70 cells / inch with a wall thickness of 0.8 mm. Twenty-six cylindrical honeycomb molded bodies (weight: 13 g) each having a cell shape and having a diameter of 1.8 cm and a length of 10 cm were prepared (total weight of the honeycomb molded bodies: 338 g).
[0035]
Then, the 26 honeycomb formed bodies were impregnated with the aqueous solution for 3 hours to obtain a carrier supporting the catalyst metal.
[0036]
Next, eight of these 26 carriers were dried under reduced pressure at 4 ° C. for 12 hours at a temperature of 50 ° C. for 12 hours using a reduced pressure dryer to evaporate and remove excess water. The support was calcined at a temperature of 500 ° C. for 4 hours under atmospheric conditions to obtain a molybdenum-supported catalyst (having a weight ratio of HZSM-5 of the entire catalyst, comprising a light yellow cylindrical honeycomb formed body). 6.8 wt% catalyst).
[0037]
Further, nine of the 26 carriers are gradually increased by spending 12 hours in a temperature range of 30 ° C. to 100 ° C. for 12 hours using a dryer with a temperature / humidity adjusting function, and the drying temperature is controlled. Moisture conditioning drying is performed while gradually lowering the humidity within the range of 90% to 0% in accordance with the degree of rise, and then sintering in the same manner as the sample S1 to form a molybdenum formed of a pale yellow cylindrical honeycomb molded body. Was prepared (a catalyst in which the weight ratio of HZSM-5 was 6.8 wt% based on the entire catalyst).
[0038]
The remaining nine of the 26 carriers were dried using a dryer with a temperature control function while gradually increasing the drying temperature from 30 ° C. to 100 ° C. for 12 hours, and then drying the sample S1. By calcination in the same manner as described above, a sample P of a catalyst (catalyst having a weight ratio of HZSM-5 of 6.8 wt% with respect to the whole catalyst) formed of a light yellow cylindrical honeycomb formed body and supporting molybdenum was obtained. Produced.
[0039]
The samples S1, S2, and P prepared as described above were respectively filled in a reaction tube (18 mm in inner diameter) made of a calorizing treatment in an inconel 800H gas-contacting part of a fixed bed flow type reaction device, and the reaction temperature in the reaction tube was set to 750. C., the pressure was set to 0.3 MPa, and the methane reaction gas was supplied at a space velocity of 3000 ml / hr / g-MFI, so that the benzene and hydrogen gas generation reaction activities due to the methane aromatization reaction were respectively reduced. Examined. The
[0040]
[Table 1]
As shown in Table 1 and FIG. 1, it can be seen that the benzene generation rate and the hydrogen gas generation rate when the samples S1 and S2 were used were higher than those of the sample P, and were particularly excellent when the sample S2 was used. Results were obtained.
[0042]
Therefore, as in the present embodiment, the carrier on which the catalyst metal such as molybdenum or the like is carried is dried under reduced pressure or controlled humidity to remove excess water by evaporation, thereby suppressing the aggregation of the catalyst metal and reducing the catalytic activity. It was confirmed that a high catalyst was obtained. In addition, it was confirmed that the use of the catalyst described above can convert lower hydrocarbons such as methane into aromatic compounds such as benzene and hydrogen gas at a high production rate.
[0043]
As described above, in the present invention, only the described specific examples have been described in detail, but it is apparent to those skilled in the art that various modifications and variations are possible within the technical idea of the present invention. It is obvious that such changes and modifications belong to the scope of the claims.
[0044]
For example, in this example, molybdenum is used as the catalyst metal, but the effect as a catalyst for converting lower hydrocarbons to an aromatic compound has already been confirmed, and is described in the literature (for example, “Surface” vol. 37 No. 12 (1999) 71). Pp.-81, “Catalytic Chemical Conversion of Methane-Direct Synthesis of Benzene Using Template Zeolite Catalysts”), rhenium, tungsten, iron, cobalt, and those (including molybdenum) It could be confirmed that the same action and effect were obtained even when the compounds were used alone or in combination.
[0045]
Further, in the present embodiment, only the method for drying the support on which the catalyst metal is supported by the impregnation method is shown. However, the same operation and effect can be obtained even when the method is applied to the support on which the catalyst metal is supported by the ion exchange method. It was confirmed that it could be obtained.
[0046]
Furthermore, in this example, a honeycomb-shaped carrier was used, but it was confirmed that the same operation and effect could be obtained when a powder-shaped, pellet-shaped, or ring-shaped carrier was used.
[0047]
【The invention's effect】
As described above, according to the present invention, by drying the support on which the catalyst metal is supported under reduced pressure or controlled humidity, the water content of the support is gradually evaporated and removed, and the catalyst supported on the support is supported. It is considered that aggregation of metal can be prevented, and as a result, a catalyst having high catalytic ability can be obtained. In addition, by using the above-mentioned catalyst, for example, the conversion of lower hydrocarbons to aromatic compounds and hydrogen gas is improved. Therefore, the conversion of lower hydrocarbons such as natural gas into chemical products such as chemicals, chemicals and plastics It is possible to efficiently produce an aromatic compound containing benzene and naphthalenes as main components, and high-purity hydrogen gas.
[Brief description of the drawings]
FIG. 1 is a graph showing a production rate characteristic with respect to a reaction elapsed time of each sample in this example.
Claims (5)
前記担持体の乾燥は、減圧雰囲気下にて行うことを特徴とする低級炭化水素の芳香族化合物化触媒の製造方法。A method for producing a catalyst for converting a lower hydrocarbon into an aromatic compound, in which a catalyst metal is supported on a metallosilicate support by an impregnation method or an ion exchange method to obtain a support, and the support is dried, water is removed, and calcined. At
The method for producing a catalyst for converting a lower hydrocarbon into an aromatic compound, wherein the drying of the support is performed under a reduced pressure atmosphere.
前記担持体の乾燥は、その乾燥温度を徐々に上昇させると共に、その乾燥温度の上昇度合いに応じて湿度を徐々に降下させながら行うことを特徴とする低級炭化水素の芳香族化合物化触媒の製造方法。A method for producing a catalyst for converting a lower hydrocarbon into an aromatic compound, in which a catalyst metal is supported on a metallosilicate support by an impregnation method or an ion exchange method to obtain a support, and the support is dried, water is removed, and calcined. At
The method for producing a catalyst for converting a lower hydrocarbon into an aromatic compound, wherein the drying of the support is performed while gradually increasing the drying temperature and gradually lowering the humidity in accordance with the degree of increase in the drying temperature. Method.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005279508A (en) * | 2004-03-30 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Three-dimensional structure pre-drying treatment method, exhaust gas purification filter and method for producing the same |
| WO2006006480A1 (en) * | 2004-07-08 | 2006-01-19 | Sued-Chemie Catalysts Japan, Inc. | Catalyst for aromatization of lower hydrocarbon and process for producing aromatic hydrocarbon and hydrogen from lower hydrocarbon with the same |
| JP2006249065A (en) * | 2005-02-10 | 2006-09-21 | Masaru Ichikawa | Method for producing aromatic hydrocarbon |
| JP2007075796A (en) * | 2005-09-16 | 2007-03-29 | Masaru Ichikawa | Lower hydrocarbon reforming catalyst |
| WO2009020045A1 (en) | 2007-08-03 | 2009-02-12 | Mitsui Chemicals, Inc. | Process for production of aromatic hydrocarbons |
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2002
- 2002-09-06 JP JP2002260706A patent/JP4302954B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005279508A (en) * | 2004-03-30 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Three-dimensional structure pre-drying treatment method, exhaust gas purification filter and method for producing the same |
| WO2006006480A1 (en) * | 2004-07-08 | 2006-01-19 | Sued-Chemie Catalysts Japan, Inc. | Catalyst for aromatization of lower hydrocarbon and process for producing aromatic hydrocarbon and hydrogen from lower hydrocarbon with the same |
| JP2006043686A (en) * | 2004-07-08 | 2006-02-16 | Sud-Chemie Catalysts Inc | Aromatization catalyst for lower hydrocarbon and method for producing aromatic hydrocarbon and hydrogen from lower hydrocarbon using it |
| JP2006249065A (en) * | 2005-02-10 | 2006-09-21 | Masaru Ichikawa | Method for producing aromatic hydrocarbon |
| JP2007075796A (en) * | 2005-09-16 | 2007-03-29 | Masaru Ichikawa | Lower hydrocarbon reforming catalyst |
| WO2009020045A1 (en) | 2007-08-03 | 2009-02-12 | Mitsui Chemicals, Inc. | Process for production of aromatic hydrocarbons |
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