JP2015229125A - Method for pretreating hydrocarbon reforming catalyst, hydrocarbon reforming catalyst, and method for reforming hydrocarbon - Google Patents
Method for pretreating hydrocarbon reforming catalyst, hydrocarbon reforming catalyst, and method for reforming hydrocarbon Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 120
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 120
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 116
- 238000002407 reforming Methods 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007789 gas Substances 0.000 claims abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000006057 reforming reaction Methods 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910002367 SrTiO Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- -1 lanthanum aluminate Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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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Abstract
Description
本発明は、炭化水素系の原料ガスを、水蒸気および二酸化炭素を用いて改質し、水素と一酸化炭素とを含む合成ガスを生成するために用いられる、炭化水素改質触媒、その前処理方法、および炭化水素改質触媒を用いた炭化水素改質方法に関する。 The present invention relates to a hydrocarbon reforming catalyst used for reforming a hydrocarbon-based raw material gas with steam and carbon dioxide to produce a synthesis gas containing hydrogen and carbon monoxide, and a pretreatment thereof The present invention relates to a method and a hydrocarbon reforming method using a hydrocarbon reforming catalyst.
石油精製や石油化学などの技術分野では種々の炭化水素系ガスが発生するが、必ずしも効率よく種々の物質の原料ガスなどとして利用できておらず、より有効な物質に変換する方法が求められている。 Various hydrocarbon gases are generated in technical fields such as petroleum refining and petrochemistry, but they are not necessarily efficiently used as raw material gases for various substances, and a method for converting them into more effective substances is required. Yes.
このような状況の下で、炭化水素系ガスを改質することによって水素および一酸化炭素を含む合成ガスを製造する方法として、炭化水素の二酸化炭素改質、炭化水素の水蒸気改質、炭化水素の部分酸化反応が知られており、石油精製や石油化学プロセスはもちろん、燃料電池向け燃料の生成プロセスにおいても利用されている。 Under such circumstances, as a method for producing a synthesis gas containing hydrogen and carbon monoxide by reforming a hydrocarbon-based gas, carbon dioxide reforming of hydrocarbon, steam reforming of hydrocarbon, hydrocarbon The partial oxidation reaction is known, and is used not only in oil refining and petrochemical processes, but also in fuel cell production processes.
炭化水素改質は、メタンなどの飽和炭化水素と二酸化炭素とを触媒の存在下に反応させ、比較的一酸化炭素濃度の高い合成ガスを製造するのに適している。 Hydrocarbon reforming is suitable for producing a synthesis gas having a relatively high carbon monoxide concentration by reacting a saturated hydrocarbon such as methane with carbon dioxide in the presence of a catalyst.
一方、炭化水素の水蒸気改質は、メタンなどの飽和炭化水素と水蒸気とを触媒の存在下に反応させ、比較的水素濃度の高い合成ガスを製造するのに適している。 On the other hand, steam reforming of hydrocarbons is suitable for producing a synthesis gas having a relatively high hydrogen concentration by reacting a saturated hydrocarbon such as methane with steam in the presence of a catalyst.
また、メタンなどの飽和炭化水素に対して二酸化炭素と水蒸気の両方を触媒の存在下に反応させる二酸化炭素と水蒸気の併用改質の方法には、二酸化炭素と水蒸気の割合を調整することで、製造される合成ガスの水素と一酸化炭素の比を調整できるという利点がある。 In addition, in the method of combined reforming of carbon dioxide and steam in which both carbon dioxide and steam react with saturated hydrocarbons such as methane in the presence of a catalyst, by adjusting the ratio of carbon dioxide and steam, There is an advantage that the ratio of hydrogen and carbon monoxide in the produced synthesis gas can be adjusted.
これら炭化水素系ガスの改質では、炭化水素が分解する過程で触媒上に炭素が析出することがある。この炭素析出の程度は炭化水素改質条件によって異なり、炭化水素の二酸化炭素改質においては最も炭素が析出しやすく、炭化水素の水蒸気改質では比較的炭素析出量が少ないと言われている。しかしながら、触媒上に析出する炭素は徐々に蓄積して触媒活性を低下させ、多量に析出した場合には反応管を閉塞させるおそれがあり、炭化水素の水蒸気改質においても、一般的には水蒸気と炭化水素の比（以下「水蒸気／炭化水素比」）を高く設定し、水蒸気を過剰に導入することにより炭素析出を抑制している。 In the reforming of these hydrocarbon gases, carbon may be deposited on the catalyst during the process of hydrocarbon decomposition. The degree of carbon deposition varies depending on the hydrocarbon reforming conditions. It is said that carbon is most likely to precipitate in carbon dioxide reforming of hydrocarbons, and that the amount of carbon deposition is relatively small in hydrocarbon steam reforming. However, the carbon deposited on the catalyst gradually accumulates to reduce the catalytic activity, and if it is deposited in large quantities, the reaction tube may be clogged. And hydrocarbon ratio (hereinafter, “steam / hydrocarbon ratio”) is set high, and carbon deposition is suppressed by introducing excessive steam.
このような炭化水素の改質に用いられる触媒としては、アルミナなどの基体にニッケルを担持させたニッケル系触媒、ルテニウムを担持させたルテニウム系触媒（特許文献１参照）、さらには、アルミナなどの基体にロジウムを担持させたロジウム系触媒（特許文献２参照）などが知られている。 Examples of the catalyst used for reforming such hydrocarbons include nickel-based catalysts in which nickel is supported on a substrate such as alumina, ruthenium-based catalysts in which ruthenium is supported (see Patent Document 1), and further, alumina and the like. A rhodium-based catalyst in which rhodium is supported on a substrate (see Patent Document 2) is known.
また、炭素析出の抑制と低温での活性向上を目的に、ペロブスカイト型複合酸化物であるアルミン酸ランタン、チタン酸ストロンチウム、チタン酸バリウムを用いた担体上に、ロジウム、コバルト、およびニッケルを活性成分として担持した触媒（特許文献３参照）が知られている。 In addition, for the purpose of suppressing carbon deposition and improving activity at low temperatures, rhodium, cobalt, and nickel are used as active ingredients on a support using lanthanum aluminate, strontium titanate, and barium titanate, which are perovskite complex oxides. A catalyst supported as (see Patent Document 3) is known.
また、上記のようなペロブスカイト型複合酸化物とニッケルからなる触媒の製造方法としては、クエン酸法によりペロブスカイト型複合酸化物担体のみを合成した後に、硝酸Ｎｉなどの溶液を用いてＮｉ成分を含侵させる方法（特許文献３）がある。 In addition, as a method for producing a catalyst composed of the perovskite complex oxide and nickel as described above, only a perovskite complex oxide support is synthesized by the citric acid method, and then a Ni component is contained using a solution such as Ni nitrate. There is a method of invading (Patent Document 3).
また、含侵工程を用いない触媒の製造方法としては、担体成分とともにＮｉ化合物を混合、焼成して触媒を製造する混錬法がある。 As a method for producing a catalyst without using an impregnation process, there is a kneading method in which a Ni compound is mixed with a carrier component and calcined to produce a catalyst.
さらに、固相合成により担体成分であるＳｒＴｉＯ3中にＮｉＯを固溶させることでＮｉ成分の分散性を向上させる方法も提案されている（特許文献４）。 Furthermore, a method of improving the dispersibility of the Ni component by dissolving NiO in the carrier component SrTiO 3 by solid phase synthesis has been proposed (Patent Document 4).
一般に、炭化水素改質触媒は、担持された金属成分が炭化水素を吸着し、分解／反応することで改質反応が進行する。しかしながら、コバルトやニッケルを使用する炭化水素改質触媒では、触媒製造時の熱処理によってコバルトやニッケルが酸化物の状態となっていることが多く、触媒活性を発現するためには、水素や炭化水素などの還元ガス雰囲気中で熱処理を行うことで、コバルトやニッケルを金属化する必要がある。 In general, in a hydrocarbon reforming catalyst, a supported metal component adsorbs hydrocarbons and decomposes / reacts so that a reforming reaction proceeds. However, in hydrocarbon reforming catalysts using cobalt and nickel, cobalt and nickel are often in an oxide state by heat treatment at the time of catalyst production. It is necessary to metallize cobalt and nickel by performing heat treatment in a reducing gas atmosphere such as.
特に、低温や低圧の条件において炭化水素の改質反応を実施する場合には、導入する炭化水素によってコバルトやニッケルが十分に還元されない可能性があるため、事前に還元前処理を行うことが好ましい。 In particular, when a hydrocarbon reforming reaction is performed under conditions of low temperature and low pressure, it is preferable to perform a reduction pretreatment in advance because cobalt or nickel may not be sufficiently reduced by the introduced hydrocarbon. .
しかしながら、チタン酸ストロンチウムなどのペロブスカイト型複合酸化物担体にコバルトやニッケルなどの卑金属を担持させた触媒では、金属成分と担体との相互作用が強いために、一般的な還元前処理によりコバルトやニッケルを金属化するだけでは十分な触媒活性が得られない場合がある。 However, in a catalyst in which a base metal such as cobalt or nickel is supported on a perovskite type complex oxide support such as strontium titanate, the interaction between the metal component and the support is strong. In some cases, sufficient catalytic activity may not be obtained simply by metallizing.
本発明は、上記課題を解決するものであり、８００℃未満の低温で、炭化水素系ガスを、水蒸気および二酸化炭素を用いて改質し、効率よく、水素と一酸化炭素とを含む合成ガスを生成させることが可能な、炭化水素改質触媒、特性の良好な炭化水素改質触媒を得るための前処理方法、および、炭化水素改質触媒を用いて効率よく改質を行うための炭化水素改質方法を提供することを目的とする。 The present invention solves the above-mentioned problem, and reforms a hydrocarbon gas with water vapor and carbon dioxide at a low temperature of less than 800 ° C., and efficiently comprises a synthesis gas containing hydrogen and carbon monoxide. Reforming catalyst, a pretreatment method for obtaining a hydrocarbon reforming catalyst with good characteristics, and carbonization for efficiently reforming using the hydrocarbon reforming catalyst An object is to provide a hydrogen reforming method.
上記課題を解決するために、本発明の炭化水素炭素改質触媒の前処理方法は、 炭化水素系ガスを、８００℃未満の温度域において、水蒸気および二酸化炭素を用いて改質し、水素と一酸化炭素とを含む合成ガスを生成するために用いられる、金属とペロブスカイト型複合酸化物とを主成分とする炭化水素改質触媒の前処理方法であって、
前記炭化水素改質触媒を、炭化水素または水素と、二酸化炭素とを含む気流中において８００℃以上の温度で加熱処理して活性化すること
を特徴としている。
In order to solve the above-mentioned problems, the hydrocarbon carbon reforming catalyst pretreatment method of the present invention reforms a hydrocarbon gas using steam and carbon dioxide in a temperature range of less than 800 ° C. A method for pretreating a hydrocarbon reforming catalyst mainly comprising a metal and a perovskite complex oxide, which is used to generate a synthesis gas containing carbon monoxide,
The hydrocarbon reforming catalyst is activated by heat treatment at a temperature of 800 ° C. or higher in an air stream containing hydrocarbon or hydrogen and carbon dioxide.
また、本発明の炭化水素炭素改質触媒の前処理方法においては、前記加熱処理の温度が９００℃以上であることがより好ましい。 In the pretreatment method for a hydrocarbon carbon reforming catalyst of the present invention, the temperature of the heat treatment is more preferably 900 ° C. or higher.
上記構成を備えることにより、高い触媒活性を備えた炭化水素炭素改質触媒を得ることが可能になる。 By providing the above configuration, a hydrocarbon carbon reforming catalyst having high catalytic activity can be obtained.
また、本発明の炭化水素炭素改質触媒の前処理方法においては、前記炭化水素改質触媒を構成する前記金属がニッケルであり、前記ペロブスカイト型複合酸化物がチタン酸ストロンチウムであることが好ましい。 In the pretreatment method for a hydrocarbon carbon reforming catalyst of the present invention, it is preferable that the metal constituting the hydrocarbon reforming catalyst is nickel, and the perovskite complex oxide is strontium titanate.
上記構成を備えることにより、高い触媒活性を備えた炭化水素改質触媒をより確実に得ることが可能になる。 By providing the above configuration, a hydrocarbon reforming catalyst having high catalytic activity can be obtained more reliably.
また、本発明の炭化水素改質触媒は、
炭化水素系ガスを、８００℃未満の温度域において、水蒸気および二酸化炭素を用いて改質し、水素と一酸化炭素とを含む合成ガスを生成するために用いられる炭化水素改質触媒であって、
ニッケルとチタン酸ストロンチウムとを主成分として含有し、ＣＯ吸着量が０．００３ｃｃ／ｇ以上であること
を特徴としている。
The hydrocarbon reforming catalyst of the present invention is
A hydrocarbon reforming catalyst used for reforming a hydrocarbon-based gas with steam and carbon dioxide in a temperature range of less than 800 ° C. to produce a synthesis gas containing hydrogen and carbon monoxide. ,
It is characterized by containing nickel and strontium titanate as main components and having a CO adsorption amount of 0.003 cc / g or more.
また、本発明の炭化水素改質触媒においては、前記ＣＯ吸着量が０．００５ｃｃ／ｇ以上であることがより好ましい。 In the hydrocarbon reforming catalyst of the present invention, the CO adsorption amount is more preferably 0.005 cc / g or more.
上記構成を備えることにより、より高い触媒活性を備えた、炭化水素改質触媒を提供することが可能になる。 By providing the above configuration, it is possible to provide a hydrocarbon reforming catalyst having higher catalytic activity.
また、本発明の炭化水素改質触媒は、炭酸ストロンチウム粉末と、酸化チタン粉末と、酸化ニッケル粉末とを含む混合原料を焼成して合成する、固相合成法により製造されるものであることが好ましい。 The hydrocarbon reforming catalyst of the present invention is manufactured by a solid-phase synthesis method in which a mixed raw material containing strontium carbonate powder, titanium oxide powder, and nickel oxide powder is fired and synthesized. preferable.
上記構成を備えることにより、効率よく製造することが可能で、高い触媒活性を備えた炭化水素改質触媒を得ることが可能になる。 By providing the above configuration, it is possible to efficiently produce a hydrocarbon reforming catalyst having high catalytic activity.
また、本発明の炭化水素改質方法は、
上記本発明の炭化水素改質触媒の前処理方法で前処理を行った炭化水素改質触媒、または、上記本発明の炭化水素改質触媒を使用し、８００℃未満の温度域において、炭化水素系ガスを、水蒸気および二酸化炭素を用いて改質し、水素と一酸化炭素とを含む合成ガスを生成すること
を特徴としている。
Moreover, the hydrocarbon reforming method of the present invention comprises:
The hydrocarbon reforming catalyst pretreated by the hydrocarbon reforming catalyst pretreatment method of the present invention or the hydrocarbon reforming catalyst of the present invention is used, and the hydrocarbon is used in a temperature range of less than 800 ° C. The system gas is reformed with water vapor and carbon dioxide to produce a synthesis gas containing hydrogen and carbon monoxide.
本発明の炭化水素炭素改質触媒の前処理方法は、上述のように、金属とペロブスカイト型複合酸化物とを主成分とする炭化水素改質触媒を、炭化水素または水素と、二酸化炭素とを含む気流中において８００℃以上の温度で加熱処理して活性化するようにしているので、炭化水素系ガスを、８００℃未満の温度域において、水蒸気および二酸化炭素を用いて改質し、水素と一酸化炭素とを含む合成ガスを生成するために用いた場合に、高い触媒活性を発揮する炭化水素改質触媒を得ることが可能になる。 As described above, the hydrocarbon carbon reforming catalyst pretreatment method of the present invention comprises a hydrocarbon reforming catalyst mainly composed of a metal and a perovskite-type composite oxide, a hydrocarbon or hydrogen, and carbon dioxide. Since it is activated by heat treatment at a temperature of 800 ° C. or higher in the air stream containing it, the hydrocarbon gas is reformed using water vapor and carbon dioxide in a temperature range of less than 800 ° C. When used to produce synthesis gas containing carbon monoxide, it is possible to obtain a hydrocarbon reforming catalyst that exhibits high catalytic activity.
言い換えると、本発明にかかる前処理方法を実施することにより、触媒の活性が向上するため、８００℃未満の低温改質条件においてもニッケルなどの金属と、チタン酸ストロンチウムなどのペロブスカイト型複合酸化物を主成分とする炭化水素改質触媒を使用して炭化水素系ガスの改質を効率よく行うことが可能になる。 In other words, since the activity of the catalyst is improved by carrying out the pretreatment method according to the present invention, a metal such as nickel and a perovskite complex oxide such as strontium titanate even under low temperature reforming conditions of less than 800 ° C. The hydrocarbon-based gas can be efficiently reformed by using the hydrocarbon reforming catalyst whose main component is.
例えば、ニッケルとチタン酸ストロンチウムを主成分とする炭化水素改質触媒の表面には、水素による還元前処理のみでは解消できない吸着阻害が存在すると考えられるが、炭化水素または水素と、二酸化炭素とを含む気流中において８００℃以上の温度で加熱処理を行う（高温の前処理を実施する）ことにより、吸着阻害が解消され、その結果として、触媒活性が向上するものと推測される。 For example, the surface of a hydrocarbon reforming catalyst mainly composed of nickel and strontium titanate is considered to have an adsorption inhibition that cannot be eliminated only by reduction pretreatment with hydrogen, but hydrocarbon or hydrogen and carbon dioxide are mixed. By performing heat treatment at a temperature of 800 ° C. or higher in the air stream that is contained (performing high temperature pretreatment), it is estimated that the adsorption inhibition is eliminated, and as a result, the catalytic activity is improved.
なお、本発明の炭化水素改質触媒を構成する金属としては、ニッケルが好ましいが、ニッケル以外にも、コバルト、鉄などを用いることが可能である。
また、本発明の炭化水素改質触媒を構成するペロブスカイト型複合酸化物としては、チタン酸ストロンチウムが好ましいが、チタン酸ストロンチウム以外にも、チタン酸バリウム、チタン酸カルシウム、ジルコン酸ストロンチウムなどを用いることができる。
In addition, as a metal which comprises the hydrocarbon reforming catalyst of this invention, although nickel is preferable, cobalt, iron, etc. can be used besides nickel.
Further, as the perovskite type complex oxide constituting the hydrocarbon reforming catalyst of the present invention, strontium titanate is preferable, but besides strontium titanate, barium titanate, calcium titanate, strontium zirconate, etc. should be used. Can do.
また、本発明の炭化水素改質触媒は、上述のように、ニッケルとチタン酸ストロンチウムとを主成分とし、ＣＯ吸着量が０．００３ｃｃ／ｇ以上であるという要件を備えているので、炭化水素系ガスを、８００℃未満の温度域において、水蒸気および二酸化炭素を用いて改質する際における高い触媒活性を備えた炭化水素改質触媒を実現することが可能になる。 Further, as described above, the hydrocarbon reforming catalyst of the present invention is mainly composed of nickel and strontium titanate and has a requirement that the CO adsorption amount is 0.003 cc / g or more. It becomes possible to realize a hydrocarbon reforming catalyst having high catalytic activity when reforming the system gas with steam and carbon dioxide in a temperature range of less than 800 ° C.
また、本発明の炭化水素改質方法は、本発明の方法で前処理を行った炭化水素改質触媒、または、本発明の炭化水素改質触媒を使用し、８００℃未満の温度域において、炭化水素系ガスを水蒸気および二酸化炭素を用いて改質し、水素と一酸化炭素とを含む合成ガスを生成するようにしているので、８００℃未満という低温で、効率よく炭化水素系ガスの改質を行うことができる。 Moreover, the hydrocarbon reforming method of the present invention uses the hydrocarbon reforming catalyst pretreated by the method of the present invention or the hydrocarbon reforming catalyst of the present invention, and in a temperature range of less than 800 ° C., The hydrocarbon gas is reformed with water vapor and carbon dioxide to produce a synthesis gas containing hydrogen and carbon monoxide, so the hydrocarbon gas can be efficiently modified at a low temperature of less than 800 ° C. Quality can be done.
以下に本発明の実施形態を示して、本発明の特徴とするところをさらに詳しく説明する。 Embodiments of the present invention will be described below to describe the features of the present invention in more detail.
［実施形態］
＜炭化水素改質触媒の作製＞
炭酸ストロンチウム（ＳｒＣＯ3）の粉末と、酸化チタン（ＴｉＯ2）の粉末をモル比で１．０：１．０となるように秤量し、さらに酸化ニッケル（ＮｉＯ）の粉末を、生成するＳｒＴｉＯ3相に対して１０．０重量％の割合となるように添加して混合した。
[Embodiment]
<Production of hydrocarbon reforming catalyst>
The powder of strontium carbonate (SrCO 3 ) and the powder of titanium oxide (TiO 2 ) are weighed so that the molar ratio is 1.0: 1.0, and the powder of nickel oxide (NiO) is further produced to produce SrTiO 3. It added and mixed so that it might become a ratio of 10.0 weight% with respect to a phase.
次に、この混合物にバインダーを加えて造粒し、約２ｍｍの粒状造粒体を得た。それから、得られた粒状体を空気中において１２００℃、２ｈの条件で焼成することにより、ＮｉＯ相とＳｒＴｉＯ3相からなる炭化水素改質触媒を得た。
なお、上述の炭化水素改質触媒の製造方法が、本発明における固体合成法による炭化水素改質触媒の製造方法の一例である。
Next, a binder was added to this mixture and granulated to obtain a granular granule of about 2 mm. Then, the obtained granular material was calcined in air at 1200 ° C. for 2 hours to obtain a hydrocarbon reforming catalyst composed of a NiO phase and a SrTiO 3 phase.
In addition, the manufacturing method of the above-mentioned hydrocarbon reforming catalyst is an example of the manufacturing method of the hydrocarbon reforming catalyst by the solid synthesis method in this invention.
＜炭化水素改質触媒の活性化のための前処理＞
上述のようにして作製した炭化水素改質触媒２．０ｃｃを、図１に示す装置の反応管２内に充填し、ヒーター１により前処理を実施する温度まで加熱した。その後、３０分間温度を安定化した後に、所定の雰囲気ガスを合計１６６ｃｃ／ｍｉｎの流量で流通しながら、１時間の熱処理を実施した。
なお、熱処理後にはＮ2ガスを流通しながら室温まで触媒を冷却して取り出した。
表１に各実施例と、各比較例の前処理条件（雰囲気ガス組成と処理温度）を示す。
<Pretreatment for activation of hydrocarbon reforming catalyst>
The hydrocarbon reforming catalyst 2.0 cc produced as described above was charged into the
After the heat treatment, the catalyst was cooled to room temperature and taken out while N 2 gas was circulated.
Table 1 shows pretreatment conditions (atmospheric gas composition and treatment temperature) of each example and each comparative example.
＜触媒のＣＯ吸着量の測定＞
上記実施例と比較例の前処理を行った炭化水素改質触媒に関して、ＣＯパルス法を用いてＣＯ吸着量の測定を行った。なお、ＣＯ吸着量の測定条件は、触媒量：０．３ｇ、前処理：５％−Ｈ2／Ａｒガス、７５０℃／３０ｍｉｎ、キャリアガス：Ｈｅ、パルスガス：５％−ＣＯ／Ｈｅ、吸着測定温度：５０℃の条件を使用した。
表２に、各実施例と各比較例の前処理を行った炭化水素改質触媒のＣＯ吸着量を示す。
<Measurement of CO adsorption amount of catalyst>
With respect to the hydrocarbon reforming catalysts subjected to the pretreatments in the above examples and comparative examples, the CO adsorption amount was measured using the CO pulse method. The measurement conditions for the CO adsorption amount were: catalyst amount: 0.3 g, pretreatment: 5% -H 2 / Ar gas, 750 ° C./30 min, carrier gas: He, pulse gas: 5% -CO / He, adsorption measurement Temperature: A condition of 50 ° C. was used.
Table 2 shows the amount of CO adsorbed by the hydrocarbon reforming catalyst subjected to the pretreatment of each example and each comparative example.
＜触媒の炭化水素改質試験＞
上記の各実施例と各比較例の前処理を行った炭化水素改質触媒の触媒活性を確認するため、メタン改質試験を実施してメタン転化率を測定した。なお、ここでのメタン改質試験は、メタンを炭化水素とし、水蒸気と二酸化炭素を併用して改質反応（以下、「メタンの水蒸気・二酸化炭素の併用改質反応」ともいう）を行わせるようにした試験である。
<Catalyst hydrocarbon reforming test>
In order to confirm the catalytic activity of the hydrocarbon reforming catalyst that had been pretreated in each of the above Examples and Comparative Examples, a methane reforming test was performed to measure the methane conversion rate. In this methane reforming test, methane is used as a hydrocarbon, and steam and carbon dioxide are used together to perform a reforming reaction (hereinafter also referred to as “combined reforming reaction of methane steam and carbon dioxide”). This is the test.
メタン転化率とは、導入したメタンのうちのどれだけが改質反応によって他の物質（ここでは主に水素と一酸化炭素）に転化したかを示す値であって、表３のメタン転化率は、他の物質に転化したメタンの、導入したメタンに対する割合を百分率で示した値である。 The methane conversion rate is a value indicating how much of the introduced methane has been converted to other substances (mainly hydrogen and carbon monoxide) by the reforming reaction. Is a percentage value of the ratio of methane converted to other substances to the introduced methane.
メタン改質試験の手順としては、先ず触媒１ｃｃを図１に示す装置の反応管２内に充填し、ヒーター１により７００℃の温度まで加熱した。その後、３０分間温度を安定させた後、ＣＨ4：Ｈ2Ｏ：ＣＯ2＝１．０：１．０：１．０の割合の混合ガスを８３ｃｃ／ｍｉｎの流量で流通しながら、３時間の改質反応を行わせた。
なお、試験中は反応管出口５から得られたガスを分析装置に導入してガス濃度を測定し、メタン転化率を算出した。
表３に、各実施例と各比較例の前処理を行った炭化水素改質触媒の、上記方法で行ったメタン改質試験におけるメタン転化率を示す。
なお、参考のため前処理を実施していない炭化水素改質触媒に関しても同様の改質試験を行った。その結果を表３に併せて示す。
As a procedure for the methane reforming test, first, 1 cc of catalyst was charged into the
During the test, the gas obtained from the
Table 3 shows the methane conversion rate in the methane reforming test conducted by the above-described method for the hydrocarbon reforming catalysts subjected to the pretreatment of each example and each comparative example.
For reference, a similar reforming test was conducted for a hydrocarbon reforming catalyst that had not been pretreated. The results are also shown in Table 3.
表３に示すように、比較例１のＨ2雰囲気にて前処理を行った触媒や、比較例２のＣＯ2雰囲気にて前処理を行った触媒を用いた場合、メタン転化率は前処理を行っていない触媒と同程度と低く、７００℃におけるメタン改質試験（メタンの水蒸気・二酸化炭素の併用改質反応）において十分な触媒活性が得られないことが確認された。 As shown in Table 3, when the catalyst pretreated in the H 2 atmosphere of Comparative Example 1 or the catalyst pretreated in the CO 2 atmosphere of Comparative Example 2 was used, the methane conversion was pretreated. It was confirmed that sufficient catalytic activity could not be obtained in a methane reforming test (combined reforming reaction of methane with steam and carbon dioxide) at 700 ° C., which is as low as that of the catalyst not subjected to the above.
一方、実施例３および実施例４のＨ2とＣＯ2とを含む雰囲気にて前処理を行った触媒を用いた場合には、比較例の条件で前処理を行った触媒に比べて高い触媒活性が得られることが確認された。 On the other hand, when the catalyst pretreated in the atmosphere containing H 2 and CO 2 of Example 3 and Example 4 is used, the catalyst is higher than the catalyst pretreated under the conditions of the comparative example. It was confirmed that activity was obtained.
また、表３より明らかなように、同じ雰囲気で前処理を行った実施例１（前処理温度９００℃）と実施例２（前処理温度８００℃）の触媒、および実施例３（前処理温度９００℃）と実施例４の触媒（前処理温度８００℃）のメタン転化率を比較すると、いずれも前処理温度が高い触媒（実施例１および３）のほうが、メタン転化率が高くなっており、高温で前処理を実施したほうが高い触媒活性が実現されることが確認された。 Further, as is apparent from Table 3, the catalyst of Example 1 (pretreatment temperature 900 ° C.) and Example 2 (pretreatment temperature 800 ° C.) that was pretreated in the same atmosphere, and Example 3 (pretreatment temperature) 900 ° C.) and the catalyst of Example 4 (pretreatment temperature 800 ° C.), the methane conversion is higher in the catalysts (Examples 1 and 3) having higher pretreatment temperatures. It was confirmed that high catalytic activity was achieved when the pretreatment was performed at a high temperature.
なお、実施例１および実施例２の上述の前処理条件は、下記の式（１）に示す、メタンのＣＯ2改質反応が進行する条件である。
また、実施例３および実施例４の前処理条件は、下記の式（２）に示す、水生逆シフト反応が進行する条件である。
The above-described pretreatment conditions of Example 1 and Example 2 are conditions under which the CO 2 reforming reaction of methane proceeds as shown in the following formula (1).
The pretreatment conditions of Example 3 and Example 4 are conditions under which the aquatic reverse shift reaction proceeds as shown in the following formula (2).
したがって、ＮｉＯ相とＳｒＴｉＯ3相からなる炭化水素改質触媒を活性化するための前処理条件としては、触媒を使用する温度域（この実施形態では７００℃）よりも高い温度域（８００℃以上）において、ＣＨ4やＨ2などの還元性ガスと、ＣＯ2の様な酸素を含有するガスとの反応が進行する雰囲気であることが好ましいと考えられる。
ＣＨ4＋ＣＯ2 ⇒ ２Ｈ2＋２ＣＯ ……（１）
Ｈ2＋ＣＯ2 ⇒ Ｈ2Ｏ＋ＣＯ ……（２）
Therefore, the pretreatment conditions for activating the hydrocarbon reforming catalyst composed of the NiO phase and the SrTiO 3 phase are higher than the temperature range where the catalyst is used (700 ° C. in this embodiment) (800 ° C. or higher). ), An atmosphere in which a reaction between a reducing gas such as CH 4 or H 2 and a gas containing oxygen such as CO 2 proceeds is preferable.
CH 4 + CO 2 ⇒ 2H 2 + 2CO (1)
H 2 + CO 2 ⇒ H 2 O + CO (2)
また、表３より、前処理を行った触媒のＣＯ吸着量の値が大きいほど、メタン改質試験を実施してメタン転化率が高くなる傾向があることがわかる。
したがって、ＮｉＯ相とＳｒＴｉＯ3相からなる炭化水素系ガス改質触媒の前処理による活性化状態は、ＣＯ吸着量により推察することが可能であり、少なくとも０．００３ｃｃ／ｇ−ｃａｔ（触媒）以上、望ましくは０．００５ｃｃ／ｇ−ｃａｔ（触媒）以上のＣＯ吸着量であることが好ましい。
Further, it can be seen from Table 3 that the larger the value of the CO adsorption amount of the pretreated catalyst, the higher the methane conversion rate by performing the methane reforming test.
Therefore, the activation state by the pretreatment of the hydrocarbon gas reforming catalyst composed of the NiO phase and the SrTiO 3 phase can be inferred from the CO adsorption amount, and is at least 0.003 cc / g-cat (catalyst) or more. Desirably, the CO adsorption amount is 0.005 cc / g-cat (catalyst) or more.
なお、上記改質試験では、メタンを炭化水素系ガスとし、これを水蒸気および二酸化炭素を用いて改質するようにした場合を例にとって説明したが、炭化水素系ガスの種類はメタンに限られるものではなく、エタン、プロパン、ブタンなど、種々の炭化水素系ガスを改質する場合にも本発明を適用することが可能である。 In the above reformation test, the case where methane is a hydrocarbon gas and the gas is reformed using steam and carbon dioxide has been described as an example. However, the type of hydrocarbon gas is limited to methane. The present invention can also be applied to reforming various hydrocarbon gases such as ethane, propane, and butane.
本発明はさらにその他の点においても、上記の実施形態に限定されるものではなく、発明の範囲内において、種々の応用、変形を加えることが可能である。 The present invention is not limited to the above-described embodiment in other points, and various applications and modifications can be made within the scope of the invention.
１ 反応管
２ ヒーター
３ 改質用触媒
４ 反応管の入口
５ 反応管の出口
1
Claims (7)
前記炭化水素改質触媒を、炭化水素または水素と、二酸化炭素とを含む気流中において８００℃以上の温度で加熱処理して活性化すること
を特徴とする炭化水素改質触媒の前処理方法。 Metal and perovskite complex oxide, which is used for reforming a hydrocarbon-based gas with water vapor and carbon dioxide in a temperature range of less than 800 ° C. to produce a synthesis gas containing hydrogen and carbon monoxide A pretreatment method of a hydrocarbon reforming catalyst mainly composed of
A pretreatment method for a hydrocarbon reforming catalyst, wherein the hydrocarbon reforming catalyst is activated by heat treatment at a temperature of 800 ° C. or higher in an air stream containing hydrocarbon or hydrogen and carbon dioxide.
ニッケルとチタン酸ストロンチウムとを主成分として含有し、ＣＯ吸着量が０．００３ｃｃ／ｇ以上であること
を特徴とする炭化水素改質触媒。 A hydrocarbon reforming catalyst used for reforming a hydrocarbon-based gas with steam and carbon dioxide in a temperature range of less than 800 ° C. to produce a synthesis gas containing hydrogen and carbon monoxide. ,
A hydrocarbon reforming catalyst comprising nickel and strontium titanate as main components and having a CO adsorption amount of 0.003 cc / g or more.
を特徴とする炭化水素改質方法。 The hydrocarbon reforming catalyst pretreated by the method according to any one of claims 1 to 3, or the hydrocarbon reforming catalyst according to any one of claims 4 to 6, and having a temperature of less than 800 ° C. A hydrocarbon reforming method characterized by reforming a hydrocarbon-based gas with water vapor and carbon dioxide in a temperature range to produce a synthesis gas containing hydrogen and carbon monoxide.
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