JP3790142B2 - Catalyst for producing carbon monoxide and ethylene from carbon dioxide and ethane and preparation method thereof - Google Patents
Catalyst for producing carbon monoxide and ethylene from carbon dioxide and ethane and preparation method thereof Download PDFInfo
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- JP3790142B2 JP3790142B2 JP2001268329A JP2001268329A JP3790142B2 JP 3790142 B2 JP3790142 B2 JP 3790142B2 JP 2001268329 A JP2001268329 A JP 2001268329A JP 2001268329 A JP2001268329 A JP 2001268329A JP 3790142 B2 JP3790142 B2 JP 3790142B2
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- catalyst
- chromium oxide
- ethylene
- ethane
- carbon monoxide
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- 239000003054 catalyst Substances 0.000 title claims description 102
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 57
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 28
- 239000005977 Ethylene Substances 0.000 title claims description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 27
- 239000001569 carbon dioxide Substances 0.000 title claims description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 43
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 8
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 8
- 229910001422 barium ion Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- -1 but in this case Chemical compound 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、二酸化炭素とエタンとの混合ガスを一酸化炭素とエチレンとを主成分とするガスに変換して一酸化炭素とエチレンとを製造する方法に用いる酸化クロム系触媒の変換特性および触媒寿命を改善した酸化クロム系触媒および該触媒の製造方法に関する。
【０００２】
【従来の技術】
エタンの脱水素反応に酸化剤として二酸化炭素を利用し、エチレンと同時に一酸化炭素を製造する方法は、既に公開特許平５-１７０６７３で提案されており、前記製造工程に触媒系として酸化クロム触媒系(S. Wang, K. Suzukiら, Appl. Catal. A: General,vol. 196，1-8(2000))を用いることは公知である。また、酸化ガリウム系（K. Nakagawa ら,Catalysis Letters, vol. 64, 215-221(2000)）、 酸化マンガン系(Y. Liuら,Stud. Surf. Sci. Catal., vol. 119, 593-597(1998))の触媒を前記製造工程に用いることも知られている。これらは、前記製造工程における有用な触媒系であるが、二酸化炭素の還元にはエタン過剰にするのが有利であるが、その場合触媒表面に炭素析出が起こり触媒の寿命を短かくしてしまうという問題があった。その対策として原料のエタンに対して５倍量の二酸化炭素を供給し、触媒寿命の向上を図っている。しかしながら、このことによって原料が希釈されるため、生成物の一酸化炭素やエチレンガスを得るには、その分大きな分離精製コストがかかるという問題があった。
【０００３】
本発明者は、前記問題、特に酸化クロム触媒系における問題を取り除くために、該触媒系に塩基性物質を添加することと該触媒系の寿命への影響を調べた。その中でＢａを加えることにより、触媒寿命に改善が見られることを見出したことを報告している（日本化学会関東支部茨城地域懇談会予稿集）。しかしながら、前記塩基性物質の添加条件と生成酸化クロム触媒系中に存在するＢａ濃度や存在形態、還元すれば新しい酸化クロム触媒系の特性との相関についての詳細な検討はなされていない。
【０００４】
【発明が解決しようとする課題】
本発明の課題は、前記従来技術の問題、すなわち、触媒寿命の改善のために原料混合ガスとして二酸化炭素過剰の条件を使用しなければならないことの問題を取り除いた、寿命特性を改善した新しい酸化クロム触媒系および該触媒系の調製方法を提供することである。
換言すれば、化学量論的な二酸化炭素とエタンの比１程度の原料混合ガスからエチレンと同時に一酸化炭素を製造することができる触媒系および該触媒系の調製方法を確立することである。本発明者は、前記課題を解決するために、本発明者らが前記報告の中で提案した酸化クロム系触媒の調製法と得られる触媒の反応性および触媒系の形態との関連を多くの試行錯誤により検討した。その中で、酸化クロム系触媒の調製に用いる酸化クロム形成原料、添加する塩基性物質、特にＢａの添加原料および調製法に工夫を加えることにより前記課題を達成できることを見出した。すなわち、通常、ある触媒系に第二成分を添加する方法として、共沈法や含浸法、イオン交換法などが一般的に用いられているが、これらの方法によってもバリウム成分の添加による前記エチレンおよび一酸化炭素の製造反応に対する長寿命化の効果はあるが、本発明の調製原料および添加方法を含めた調製方法の工夫により、従来の形態とは異なる酸化クロム系触媒の調製が可能であり、前記形態の違いに基づくものと考えられる、前記エチレンおよび一酸化炭素の製造における化学量論的反応性および触媒の長寿命化を達成することができることを見出した。
【０００５】
【課題を解決するための手段】
本発明の第１は、二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンとを製造する方法に用いる酸化クロム系触媒において、該触媒系にＭ／Ｃｒ（但し、ＭはＢａまたはＳｒである。）原子比が０．０２より大きくなるようにＭイオンを分散・添加できるように調製したことを特徴とする二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンとを製造する方法に用いる酸化クロム系触媒である。好ましくは、酸化クロム系触媒において、前記Ｍ／Ｃｒ原子比が０．０５より大きくなるようにＭイオンを分散・添加できるように調製することを特徴とする前記二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンとを製造する方法に用いる酸化クロム系触媒であり、より好ましくは、Ｘ線回折による観察において、結晶を構成する原子として前記Ｍが見出されないことを特徴とする前記各二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンとを製造する方法に用いる酸化クロム系触媒であり、一層好ましくは、ＭがＢａであることを特徴とする前記各二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンとを製造する方法に用いる酸化クロム系触媒であり、より一層好ましくは、化学量論的反応においても触媒上にエタンからの炭素の生成がないことを特徴とする前記各二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンとを製造する方法に用いる酸化クロム系触媒である。
【０００６】
本発明の第２は、酸化クロムを形成する硝酸クロム九水和物と添加・分散Ｍ（但し、ＭはＢａまたはＳｒ）イオンを形成するＭ（ＯＨ）2・８Ｈ2Ｏを混合し、該混合物を水中に分散して５０℃〜９０℃に、３時間〜１２時間加温し、次いで室温まで冷却した後、上澄み液を除去する水洗を上澄み液のｐＨ値が最大になるまで繰り返し、その時点でろ過し、固形物を空気中１００℃以上で乾燥後、空気中で最高８００±１００℃で焼成することを特徴とする酸化クロム系触媒において、該触媒系にＭ／Ｃｒ原子比が０．０２より大きくなるようにＭイオンを分散・添加させたことを特徴とする二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンを製造する方法に用いる酸化クロム系触媒の調製方法である。好ましくは、Ｘ線回折による観察において、結晶を構成する原子としてＭが見出されないことを特徴とする前記二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンを製造する方法に用いる酸化クロム系触媒の調製方法であり、より好ましくは、ＭがＢａであることを特徴とする前記二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンを製造する方法に用いる酸化クロム系触媒の調製方法である。
【０００７】
【本発明の実施の態様】
本発明をより詳細に説明する。
ここでは、塩基性物質としてＢａイオンを添加した場合について説明するが、Ｓｒにおいても、同様の酸化クロム系触媒が得られおよび同様の触媒の調製方法が適用できる。
【０００８】
Ａ．触媒の調製方法。
１，酸化クロムの原料として硝酸クロム九水和物、添加イオンとして水酸化バリウム八水和物をそれぞれ用い、これらを互いによく混合する。
２，該混合物を純水に分散して５０℃〜９０℃に、３時間〜１２時間加温する。
３，冷却後、傾斜法により上澄液を除去し、これに水を加えて水洗−傾斜による上澄液除去を繰り返す。その上澄み液のｐＨ値が最大（おおよそｐＨ８〜９）になったところで水洗を止める。
４，得られた沈殿物をろ過、乾燥する。
５，乾燥したものを、焼成（例として７００℃）することにより得られる、酸化クロムにＢａ／Ｃｒ原子比が０．０２より大きくなるようにＢａイオンを分散・添加した新規な酸化クロム系触媒が得られる。
これらの工程によって得られた酸化クロム系触媒は、Ｘ線回折の観察から、結晶化度の低い酸化クロムであり、従来の塩基性物質、ここではＢａイオンの高度分散状態、すなわち、Ｂａ／Ｃｒの原子比が０．０２以上、好ましくは０．０５以上とすることができた。そして、これにより触媒の塩基性は増し、触媒表面での二酸化炭素濃度が上がり、エタンから引き抜かれた水素との反応性が増し、二酸化炭素とエタンの原料混合ガスの混合比が１：１、すなわち化学量論量の原料ガスから一酸化炭素とエチレンの混合比がほぼ１：１の生成ガスを得ることが可能とすることができた。更に、エタンを過剰にする必要が無いために、触媒表面での炭化を防ぐことができ、触媒を長寿命とすることができた。
【０００９】
【実施例】
触媒の調製。
実施例１、触媒１
硝酸クロム九水和物５２．６５ｇ(０．１３１ｍｏｌ)と水酸化バリウム八水和物６２．２５ｇ（０．１９７ｍｏｌ）を自動式の乳鉢で約１時間混合し、緑色の混練物を得る。これを純水に分散し約８０℃で数時間加温、その後冷却し傾斜法で上澄み液を捨てる。このような水洗を繰り返えして行くとｐＨが次第に上がる。ｐＨ値が最大に達したところで水洗を終了した。ろ過後、１００℃で２４時間乾燥した。さらに、空気中において最高温度７００℃で３時間焼成した。Ｂａ／Ｃｒ原子比は０．０５であり目的の触媒を得た。
【００１０】
実施例２
触媒２ 触媒１の方法で調製された触媒の内、特に沈殿物の沈殿速度が速いもの（粒子が粗いもの）をろ過・乾燥・焼成した触媒。少量のＣｒ2Ｏ3と痕跡量のＢａＣｒＯ4が認められた。Ｂａ／Ｃｒ原子比は０．０２であり目的の触媒を得た。
因みに、本発明の調製法によらない酸化クロム触媒中の塩基性物質のイオン濃度は１／７〜１／８であった。
【００１１】
参考例１
触媒３
硝酸クロム九水和物５２．６５ｇと水酸化ナトリウム１１．８４ｇ(０．３９４８ｍｏｌ)を用いて、触媒１と同様の方法で調製、焼成してＮａイオン添加触媒を得た。
触媒４
硝酸クロム九水和物５２．６５ｇと水酸化カルシウム１４．６１ｇ(０．１９７ｍｏｌ)を用いて、触媒１と同様の方法で焼成した触媒。
【００１２】
触媒５
酢酸クロム溶液１４．６１ｇを蒸発皿の中で空気中７００℃で３時間熱分解した触媒。
触媒６、７
通常のバリウムの添加法である、含浸法（６）および共沈法（７）によってＢａイオンを添加した。含浸法（６）では、Ｂａ担持量を触媒１，２のように多くすることが出来ず、また、共沈法（７）では、水洗が捗らないためにＢａイオンが残り、ＢａＣｒＯ4の高酸化状態の結晶構造が現れ触媒１，２の長寿命化を図ることができなかった。
【００１３】
実施例３、前記触媒１〜７を用いて、二酸化炭素とエタンの混合ガスから一酸化炭素とエチレンを製造した。結果を表１に示す。
反応条件
前記各触媒の活性試験は、全長５００ｍｍの石英ガラス製反応管（外径１０ｍｍφ、内径８ｍｍφ、長さ３００ｍｍの管と外径８ｍｍφ、内径６ｍｍφ、 長さ２００ｍｍの管を接合したもの）の中央部分に０．５ｇの触媒を石英ウ−ルで保持し、これに反応ガス（全流速４０ｍＬ／分、エタン：二酸化炭素：内部標準ガス(窒素)＝４５：４５：１０を供給しながら、触媒層温度７００℃での反応生成物をガスクロ分析装置（日立製作所製、６６３型ガスクロ分析装置）で分離定量した。表１に上記の反応条件での二酸化炭素ならびにエタンの転化率、および生成物の割合を体積パーセントで示す。経時変化があるため３時間後の値で比較した。
【００１４】
【表１】
前記結果から、触媒の調製におけるＢａイオンの添加方法は非常に重要であり、実施例１，２以外では、酸化クロム触媒中に高濃度のＢａイオンを分散・添加することができなかった。すなわち、実施例１，２以外ではＣｒ2Ｏ3の結晶構造が大きく現れ、Ｃｒ2Ｏ3の結晶構造の小さい本発明の触媒とは形態が全く異なる。また、Ｂａ／Ｃｒ原子比は、本発明の触媒では、１／２０以上になるのに対し、他の触媒（実施例７を除く）では、本発明の１／７〜１／８程度であった。たとえ実施例７のようにＢａ／Ｃｒ原子比が１／１０以上になってもＢａＣｒＯ4の高酸化状態の結晶構造が現れ触媒１，２の長寿命化を図ることができなかった。
実施例２の触媒では高酸化状態の痕跡量のＢａＣｒＯ4が認められたが、実質的に結晶を構成する原子としてＢａが見出されない程度である。
【００１６】
【発明の効果】
以上述べたように、本発明の酸化クロム系触媒は、二酸化炭素とエタンとの混合ガスを化学量論に近い反応により一酸化炭素とエチレンとを主成分とするガスに変換できるという特性を持ち、更にこれにより触媒寿命を改善できるという、新規な酸化クロム系触媒を提供できたという優れた効果、および該反応系に用いられる触媒中における添加イオンの存在形態を変えることにより、触媒特性を顕著に変えることができることの技術的示唆は、この分野の発展に寄与することは明らかである。また、温暖化現象における解決の道が未だ、定まらない中で、化学原料の循環使用の技術に適用すれば、大きな貢献になることは明らかである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a conversion characteristic of a chromium oxide catalyst used in a method for producing carbon monoxide and ethylene by converting a mixed gas of carbon dioxide and ethane into a gas mainly composed of carbon monoxide and ethylene, and the catalyst. The present invention relates to a chromium oxide catalyst having an improved life and a method for producing the catalyst.
[0002]
[Prior art]
A method for producing carbon monoxide simultaneously with ethylene by using carbon dioxide as an oxidant for ethane dehydrogenation has already been proposed in Japanese Patent Laid-Open No. 5-170673, and a chromium oxide catalyst is used as a catalyst system in the production process. It is known to use the system (S. Wang, K. Suzuki et al., Appl. Catal. A: General, vol. 196, 1-8 (2000)). In addition, gallium oxide (K. Nakagawa et al., Catalysis Letters, vol. 64, 215-221 (2000)), manganese oxide (Y. Liu et al., Stud. Surf. Sci. Catal., Vol. 119, 593- 597 (1998)) is also known for use in the production process. These are useful catalyst systems in the above production process, but it is advantageous to make ethane excess for the reduction of carbon dioxide, but in this case, carbon deposition occurs on the catalyst surface and the life of the catalyst is shortened. was there. As a countermeasure, carbon dioxide is supplied 5 times as much as the raw material ethane to improve the catalyst life. However, since the raw material is diluted by this, there is a problem that it takes a large amount of separation and purification cost to obtain the product carbon monoxide and ethylene gas.
[0003]
The present inventor investigated the effects of adding a basic substance to the catalyst system and the life of the catalyst system in order to remove the above problem, particularly the problem in the chromium oxide catalyst system. Among them, it has been reported that the addition of Ba has found that the catalyst life can be improved (The Chemical Society of Japan Kanto Branch Ibaraki Regional Roundtable Proceedings). However, no detailed examination has been made on the correlation between the basic substance addition conditions and the concentration and form of Ba present in the produced chromium oxide catalyst system and the characteristics of the new chromium oxide catalyst system if reduced.
[0004]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems of the prior art, that is, the new oxidation with improved life characteristics, which eliminates the problem of using carbon dioxide-excess conditions as a raw material mixed gas for improving the catalyst life. It is to provide a chromium catalyst system and a process for preparing the catalyst system.
In other words, to establish a catalyst system capable of producing carbon monoxide simultaneously with ethylene from a raw material mixed gas having a stoichiometric ratio of carbon dioxide and ethane of about 1, and to prepare the catalyst system. In order to solve the above-mentioned problems, the present inventor has made many relationships between the method of preparing the chromium oxide catalyst proposed by the present inventors in the above report and the reactivity of the resulting catalyst and the form of the catalyst system. It was examined by trial and error. Among them, it has been found that the above-mentioned problems can be achieved by devising the chromium oxide forming raw material used for the preparation of the chromium oxide catalyst, the basic substance to be added, particularly the additive raw material for Ba and the preparation method. That is, as a method for adding a second component to a catalyst system, a coprecipitation method, an impregnation method, an ion exchange method, etc. are generally used. Although there is an effect of prolonging the lifetime for the production reaction of carbon monoxide, it is possible to prepare a chromium oxide catalyst different from the conventional form by devising the preparation method including the preparation raw material and the addition method of the present invention. The inventors have found that stoichiometric reactivity and longer catalyst life can be achieved in the production of ethylene and carbon monoxide, which is believed to be based on the difference in the morphology.
[0005]
[Means for Solving the Problems]
A first aspect of the present invention is a chromium oxide-based catalyst used in a method for producing carbon monoxide and ethylene from a mixed gas of carbon dioxide and ethane, wherein the catalyst system is M / Cr (where M is Ba or Sr). .) Oxidation used in a method for producing carbon monoxide and ethylene from a mixed gas of carbon dioxide and ethane, which is prepared so that M ions can be dispersed and added so that the atomic ratio is greater than 0.02. It is a chromium-based catalyst. Preferably, the chromium oxide catalyst is prepared so that M ions can be dispersed and added so that the M / Cr atomic ratio is greater than 0.05. Each of the carbon dioxides is a chromium oxide catalyst used in a method for producing carbon oxide and ethylene, and more preferably, the M is not found as an atom constituting the crystal in observation by X-ray diffraction. Chromium oxide catalyst used in a method for producing carbon monoxide and ethylene from a mixed gas of ethane and ethane, and more preferably one of the mixed gas of carbon dioxide and ethane, wherein M is Ba. A chromium oxide-based catalyst used in a method for producing carbon oxide and ethylene, and more preferably ethane on the catalyst even in a stoichiometric reaction. Chromium oxide based catalyst for use in a method for producing carbon monoxide and ethylene from the gas mixture of the carbon dioxide and ethane, characterized in that there is no generation of carbon al.
[0006]
In the second aspect of the present invention, chromium nitrate nonahydrate that forms chromium oxide and M (OH) 2 .8H 2 O that forms added / dispersed M (where M is Ba or Sr) ions are mixed, The mixture is dispersed in water, heated to 50 ° C. to 90 ° C. for 3 to 12 hours, then cooled to room temperature, and then washed with water to remove the supernatant until the pH value of the supernatant is maximized. The chromium oxide catalyst is characterized in that it is filtered at a time point, and the solid is dried in air at 100 ° C. or higher and then calcined in air at a maximum of 800 ± 100 ° C. The catalyst system has an M / Cr atomic ratio of 0. This is a method for preparing a chromium oxide catalyst used in a method for producing carbon monoxide and ethylene from a mixed gas of carbon dioxide and ethane, wherein M ions are dispersed and added so as to be larger than 0.02. Preferably, a chromium oxide catalyst used in the method for producing carbon monoxide and ethylene from the mixed gas of carbon dioxide and ethane, wherein M is not found as an atom constituting the crystal in observation by X-ray diffraction More preferably, it is a method for preparing a chromium oxide catalyst used in the method for producing carbon monoxide and ethylene from the mixed gas of carbon dioxide and ethane, wherein M is Ba.
[0007]
[Embodiments of the present invention]
The present invention will be described in more detail.
Here, a case where Ba ions are added as a basic substance will be described, but a similar chromium oxide-based catalyst can be obtained and a similar catalyst preparation method can also be applied to Sr.
[0008]
A. Catalyst preparation method.
1, Chromium nitrate nonahydrate is used as a raw material for chromium oxide, and barium hydroxide octahydrate is used as an additive ion, and these are mixed well.
2. Disperse the mixture in pure water and warm to 50 to 90 ° C. for 3 to 12 hours.
3. After cooling, the supernatant is removed by the gradient method, water is added to this, and the supernatant is removed by washing and decanting. When the pH value of the supernatant reaches the maximum (approximately pH 8-9), the water washing is stopped.
4. Filter and dry the resulting precipitate.
5. A novel chromium oxide catalyst obtained by dispersing and adding Ba ions to chromium oxide so that the Ba / Cr atomic ratio is greater than 0.02, obtained by firing the dried one (eg, 700 ° C.). Is obtained.
From the observation of X-ray diffraction, the chromium oxide-based catalyst obtained by these steps is a chromium oxide having a low crystallinity, and is a highly dispersed state of a conventional basic substance, here, Ba ions, that is, Ba / Cr. The atomic ratio can be 0.02 or more, preferably 0.05 or more. This increases the basicity of the catalyst, increases the carbon dioxide concentration on the catalyst surface, increases the reactivity with hydrogen extracted from ethane, and the mixing ratio of carbon dioxide and ethane raw material mixed gas is 1: 1. That is, it was possible to obtain a product gas having a mixing ratio of carbon monoxide and ethylene of approximately 1: 1 from a stoichiometric amount of raw material gas. Furthermore, since there is no need to make ethane excessive, carbonization on the catalyst surface can be prevented, and the catalyst can have a long life.
[0009]
【Example】
Preparation of catalyst.
Example 1, Catalyst 1
Chromium nitrate nonahydrate 52.65 g (0.131 mol) and barium hydroxide octahydrate 62.25 g (0.197 mol) are mixed in an automatic mortar for about 1 hour to obtain a green kneaded product. This is dispersed in pure water, heated at about 80 ° C. for several hours, then cooled, and the supernatant is discarded by a gradient method. When such washing with water is repeated, the pH gradually increases. The water washing was terminated when the pH value reached the maximum. After filtration, it was dried at 100 ° C. for 24 hours. Further, it was fired in air at a maximum temperature of 700 ° C. for 3 hours. The Ba / Cr atomic ratio was 0.05, and the target catalyst was obtained.
[0010]
Example 2
Catalyst 2 A catalyst prepared by filtering, drying and calcining a catalyst prepared by the method of Catalyst 1 and having a particularly high sedimentation rate (coarse particles). A small amount of Cr 2 O 3 and a trace amount of BaCrO 4 were observed. The Ba / Cr atomic ratio was 0.02, and the target catalyst was obtained.
Incidentally, the ion concentration of the basic substance in the chromium oxide catalyst not based on the preparation method of the present invention was 1/7 to 1/8.
[0011]
Reference example 1
Catalyst 3
Using 52.65 g of chromium nitrate nonahydrate and 11.84 g (0.3948 mol) of sodium hydroxide, it was prepared and calcined in the same manner as in Catalyst 1 to obtain a Na ion addition catalyst.
Catalyst 4
A catalyst calcined in the same manner as Catalyst 1 using 52.65 g of chromium nitrate nonahydrate and 14.61 g (0.197 mol) of calcium hydroxide.
[0012]
Catalyst 5
A catalyst obtained by pyrolyzing 14.61 g of a chromium acetate solution in an evaporating dish at 700 ° C. in air for 3 hours.
Catalysts 6 and 7
Ba ions were added by an impregnation method (6) and a coprecipitation method (7), which are ordinary barium addition methods. In the impregnation method (6), the amount of Ba supported cannot be increased as in the case of the catalysts 1 and 2, and in the coprecipitation method (7), since water washing does not progress, Ba ions remain, and the high amount of BaCrO 4 An oxidation state crystal structure appeared and the life of the catalysts 1 and 2 could not be extended.
[0013]
Example 3 Carbon monoxide and ethylene were produced from a mixed gas of carbon dioxide and ethane using the catalysts 1 to 7. The results are shown in Table 1.
Reaction conditions The activity test of each of the above catalysts was performed on a reaction tube made of quartz glass having a total length of 500 mm (a tube having an outer diameter of 10 mmφ, an inner diameter of 8 mmφ, a length of 300 mm and an outer diameter of 8 mmφ, an inner diameter of 6 mmφ, and a length of 200 mm). While holding 0.5 g of catalyst in the center part with quartz wool, while supplying reaction gas (total flow rate 40 mL / min, ethane: carbon dioxide: internal standard gas (nitrogen) = 45: 45: 10, The reaction products at a catalyst layer temperature of 700 ° C. were separated and quantified by a gas chromatography analyzer (manufactured by Hitachi, Ltd., 663 gas chromatography analyzer) Table 1 shows conversion rates of carbon dioxide and ethane under the above reaction conditions, and products. The ratio was expressed as a volume percentage, and the values after 3 hours were compared because of the change over time.
[0014]
[Table 1]
From the above results, the method of adding Ba ions in the preparation of the catalyst is very important. Except for Examples 1 and 2, it was not possible to disperse and add a high concentration of Ba ions in the chromium oxide catalyst. That is, examples appear larger crystal structure of Cr 2 O 3 is 1, 2, except, totally embodiment differs from the catalyst of the crystal structure of the small present invention Cr 2 O 3. Further, the Ba / Cr atomic ratio is 1/20 or more for the catalyst of the present invention, whereas it is about 1/7 to 1/8 of the present invention for other catalysts (except for Example 7). It was. Even if the Ba / Cr atomic ratio was 1/10 or more as in Example 7, the crystal structure of BaCrO 4 in a highly oxidized state appeared and the life of the catalysts 1 and 2 could not be extended.
In the catalyst of Example 2, a trace amount of BaCrO 4 in a highly oxidized state was observed, but Ba was not found substantially as an atom constituting the crystal.
[0016]
【The invention's effect】
As described above, the chromium oxide catalyst of the present invention has a characteristic that a mixed gas of carbon dioxide and ethane can be converted into a gas mainly composed of carbon monoxide and ethylene by a reaction close to stoichiometry. In addition, the catalyst life can be improved by this, and the excellent effect that a novel chromium oxide catalyst can be provided, and the presence of added ions in the catalyst used in the reaction system is changed, thereby significantly improving the catalyst characteristics. It is clear that the technical suggestion that can be changed to contribute to the development of this field. Moreover, it is clear that if the method of recycling chemical raw materials is applied to the technology of recycling the chemical raw material, the solution for the global warming phenomenon has not yet been determined.
Claims (8)
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