JP5285776B2 - 天然ガス及び二酸化炭素からの合成ガス製造用触媒及びその製造方法 - Google Patents
天然ガス及び二酸化炭素からの合成ガス製造用触媒及びその製造方法 Download PDFInfo
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- JP5285776B2 JP5285776B2 JP2011521026A JP2011521026A JP5285776B2 JP 5285776 B2 JP5285776 B2 JP 5285776B2 JP 2011521026 A JP2011521026 A JP 2011521026A JP 2011521026 A JP2011521026 A JP 2011521026A JP 5285776 B2 JP5285776 B2 JP 5285776B2
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- 239000003054 catalyst Substances 0.000 title claims description 150
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 88
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 80
- 238000003786 synthesis reaction Methods 0.000 title claims description 69
- 230000015572 biosynthetic process Effects 0.000 title claims description 52
- 239000007789 gas Substances 0.000 title claims description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 40
- 239000001569 carbon dioxide Substances 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000003345 natural gas Substances 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 126
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 120
- 238000006057 reforming reaction Methods 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 48
- 238000002407 reforming Methods 0.000 claims description 27
- 229910004625 Ce—Zr Inorganic materials 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000629 steam reforming Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 6
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- 238000001354 calcination Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
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- 239000001099 ammonium carbonate Substances 0.000 claims description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 80
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 39
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- 230000000694 effects Effects 0.000 description 27
- 229910052759 nickel Inorganic materials 0.000 description 22
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
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- 230000009849 deactivation Effects 0.000 description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 10
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 7
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- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
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- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
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- 229910052700 potassium Inorganic materials 0.000 description 3
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000002453 autothermal reforming Methods 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- FTWGTNVTSDGLFG-UHFFFAOYSA-N nitric acid zirconium Chemical compound [Zr].O[N+]([O-])=O FTWGTNVTSDGLFG-UHFFFAOYSA-N 0.000 description 1
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Description
(1)メタンの水蒸気改質反応(SRM)
CH4+H2O=3H2+CO ΔH=226kJ/mol
⇒ 強い吸熱反応、
H2/CO>3、
過剰水蒸気が要求される
(2)メタンの部分酸化反応(POM)
CH4+0.5O2=2H2+CO ΔH=−44kJ/mol
⇒ 穏やかな発熱反応、
H2/CO=2、
O2生産工程が要求される
(3)メタンの二酸化炭素改質反応(CDR)
CH4+CO2=2H2+2CO ΔH=261kJ/mol
⇒ 強い吸熱反応、
H2/CO=1、
CO2の追加が要求される
前記個々の改質工程としては、エネルギーや炭素効率の増大とともに、適切なH2/CO比の維持のために、POM及びSRMが混合された自己熱改質反応(auto−thermal reforming;ATR)や、POM、SRM及びCDRの3つの改質反応が混合された方法である三反応型改質反応(tri−reforming)などがよく知られている。また、改質反応の種類や触媒に応じてH2/CO比が異なる合成ガスを製造することができる。これらの様々な比を有する合成ガスを利用した様々な方法に関する特許出願が、現在数多く出願されている[特許文献1及び2]。
/メタンのモル比4〜6:1の範囲で、Ni/Al2O3触媒系が主に使用されている。しかし、炭素の堆積による著しい触媒の不活性化が発生するという問題があり、貴金属又は助触媒として遷移金属及びアルカリ金属を含有する触媒系についての研究が数多く行われている[非特許文献1]。
また、本発明の他の目的は、前記触媒を使用して合成ガスを製造する方法を提供することにある。
以下、本発明をより詳細に説明する。
天然ガスの混合型改質は、二酸化炭素の経済的な活用方法である。本発明において、天然ガス(CH4)の水蒸気改質反応(steam reforming of methane;SRM)は、一酸化炭素、二酸化炭素及び水素の合成ガスが特定のモル比(H2/(2CO+3CO2)=0.85〜1.15)を維持するように、メタンの二酸化炭素改質反応(Carbon dioxide reforming of methane;CDR)と同時に実施される。この方法において、触媒(Ni/Ce(Zr)/MgAlOxとも称される)は、メタノール合成反応又はフィッシャー・トロプシュ反応に有利な合成ガスを製造するために用いられる。メタノール合成触媒としては、先行特許文献(韓国特許出願第2008−0072286号公報)に提示された副産物の生成を最小化する触媒系、及び既存の商業用Cu−ZnO−Al2O3系触媒を使用することができる。
まず、Ni/Ce(Zr)/MgAlOxで構成される触媒上において、天然ガスの水蒸気改質反応とメタンの二酸化炭素改質反応とが同時に実施される混合型改質反応によりH2/(2CO+3CO2)=0.85〜1.15を維持する。こうすることで、メタノール合成反応及びフィッシャー・トロプシュ反応にも優れた活性を示す反応条件を導入することができる。
まず、酸素貯蔵能力を有することが知られているCe成分、又は酸性部位と塩基性部位とを同時に導入して炭素の堆積を抑制することができるCe−Zr成分を導入することにより、支持体としてのMgAlOxを前処理する。これにより、改質反応中における炭素の堆積による触媒の不活性化を抑制することができる。前記前処理方法は、本研究の先行研究の結果(韓国公開特許第2002−0021721号公報、韓国公開特許第2004−0051953号公報及び韓国公開特許第2002−0088213号公報)に基づくものであり、セリウムで修飾されたジルコニア成分を使用する場合には、炭素の堆積による触媒の不活性化を抑制できることが報告されている。本発明において、使用される混合型改質触媒用支持体は、Ce(Zr)/MgAlOxで構成される成分中Ce又はCe−Zrの含量がMgAlOxの重量に対し3〜20重量%を維持するように製造される。このとき、Ce又はCe−Zrの含有量が3重量%未満の場合には、前処理による炭素の堆積の抑制効果が微々たるものであり、20重量%を超える場合には、支持体であるMgAlOxの気孔の閉塞による比表面積の減少によってNiの分散性が減少し、触媒の活性が減少する。また、MgAlOx支持体の前処理のための成分であるCe及びZrの金属の重量組成比(Zr/Ce)は、0〜4の範囲を維持するようにする。Zrの含有量が増加してZr/Ceの比が4を超える場合には、活性成分であるNiの分散性が減少して活性が低下し得るため、前記範囲を維持する必要がある。
[実施例1]
まず、MgO/Al2O3比が3/7のハイドロタルサイト構造のMgAlOx(30)支持体であるPURAL MG30(サソール社製、比表面積は250m2/g以上)を混合型改質反応用触媒の支持体として使用した。次に、酢酸セリウムを、Ce金属がMgAlOx(30)支持体に対して4重量%となるように含浸させると同時に、ニッケル前駆体として硝酸ニッケル六水和物(Ni(NO3)2・6H2O)をCe/MgAlOx(30)支持体に対し12重量%となるように担持させた。さらに、真空乾燥機中70℃で12時間攪拌して溶媒である水を除去し、100℃のオーブンで24時間以上乾燥させた後、850℃で6時間焼成して最終触媒であるNi/Ce/MgAlOx(30)を製造した。
混合型改質反応を実施する前に、触媒0.5gと希釈剤であるアルファ−アルミナ34.5gとを均一に混合してインコロイ(Incoloy)800H反応器に装入し、700℃の水素(5体積%H2/N2)雰囲気下で3時間還元処理した後に反応を実施した。CH4、CO2、H2O、N2を1:0.4:1:1(CH4:CO2:H2O:N2)の割合のモル比で含む反応物を反応器へ注入し、反応温度850℃、反応圧力1.0MPa、空間速度5000L(CH4)/kg触媒/時の条件で反応を実施した。3時間及び20時間反応させた後のメタン及び二酸化炭素の転換率並びにH2/(2CO+3CO2)モル比の2時間の平均値、及び反応20時間のH2/(2CO+3CO2)のモル比の変化率を以下の表1に示した。
MgO/Al2O3比5/5のハイドロタルサイト構造のMgAlOx(50)支持体であるPURAL MG50(サソール社製、比表面積は200m2/g以上)を使用したことを除き、実施例1と同様の方法で、最終触媒であるNi/Ce/MgAlOx(50)を製造した。このとき、触媒の比表面積は117m2/g、気孔体積は0.30cm3(cc)/g、平均気孔サイズは13.2nmであった。前記触媒を使用して実施例1と同様の方法で混合型改質反応を実施し、3時間及び20時間反応させた後のメタン及び二酸化炭素の転換率並びにH2/(2CO+3CO2)モル比の2時間の平均値、及び反応20時間のH2/(2CO+3CO2)のモル比の変化率を以下の表1に示した。
MgO/Al2O3比7/3のハイドロタルサイト構造のMgAlOx(70)支持体であるPURAL MG70(サソール社製、比表面積は180m2/g以上)を使用したことを除き、実施例1と同様の方法で、最終触媒であるNi/Ce/MgAlOx(70)を製造した。このとき、触媒の比表面積は104m2/g、気孔体積は0.24cm3(cc)/g、平均気孔サイズは11.0nmであった。前記触媒を使用して実施例1と同様の方法で混合型改質反応を実施し、3時間及び20時間反応させた後のメタン及び二酸化炭素の転換率並びにH2/(2CO+3CO2)モル比の2時間の平均値、及び反応20時間のH2/(2CO+3CO2)のモル比の変化率を以下の表1に示した。
実施例1と同様の方法で、MgO/Al2O3比3/7のハイドロタルサイト構造のMgAlOx(30)支持体であるPURAL MG30(サソール社製、比表面積は250m2/g以上)を使用し、かつ酢酸セリウム及び硝酸ジルコニウムを、Zr/Ce重量比が0.25となるようにMgAlOx(30)支持体に含浸させ、かつCe−Zrの重量がMgAlOx(30)支持体に対し18重量%となるように担持させた。同時に、ニッケル前駆体として硝酸ニッケル六水和物(Ni(NO3)2・6H2O)をCe−Zr/MgAlOx(30)支持体に対し15重量%となるように担持させ、真空乾燥機中70℃で12時間攪拌して溶媒である水を除去し、100℃のオーブンで24時間以上乾燥させた後、850℃で6時間焼成して最終触媒であるNi−Ce−Zr/MgAlOx(30)を製造した。このとき、触媒の比表面積は85m2/g、気孔体積は0.21cm3(cc)/g、平均気孔サイズは11.5nmであった。
MgO/Al2O3比3/7のハイドロタルサイト構造のMgAlOx(30)支持体であるPURAL MG30(サソール社製、比表面積は250m2/g以上)を使用し、かつ酢酸セリウム及び硝酸ジルコニウムを、Zr/Ce重量比が3となるようにMgAlOx(30)支持体に含浸させ、かつCe−Zrの重量がMgAlOx(30)支持体に対し5重量%となるように担持させた。70℃で12時間攪拌して溶媒である水を除去し、100℃のオーブンで24時間以上乾燥させた後、900℃で6時間焼成してCe−Zr/MgAlOx(30)支持体を製造した。前記製造された支持体に対し12重量%のニッケルを担持させ、70℃で12時間攪拌して溶媒である水を除去し、100℃のオーブンで24時間以上乾燥させた後、550℃で6時間焼成して最終触媒であるNi/Ce−Zr/MgAlOx(30)を製造した。このとき、触媒の比表面積は96m2/g、気孔体積は0.31cm3(cc)/g、平均気孔サイズは16.5nmであった。
MgO/Al2O3比3/7のハイドロタルサイト構造のMgAlOx(30)支持体であるPURAL MG30(サソール社製、比表面積は250m2/g以上)を使用し、ニッケルのみを支持体に対し12重量%となるように担持させたことを除き、実施例1と同様の方法でNi/MgAlOx(30)の触媒を製造した。このとき、触媒の比表面積は118m2/g、気孔体積は0.34cm3(cc)/g、平均気孔サイズは13.8nmであった。前記触媒を用いて実施例1と同様の方法で混合型改質反応を実施し、3時間及び20時間反応させた後のメタン及び二酸化炭素の転換率並びにH2/(2CO+3CO2)モル比の2時間の平均値、及び反応20時間のH2/(2CO+3CO2)のモル比の変化率を以下の表1に示した。
前記実施例4と同様の方法で、比表面積が200m2/gのサソール社のガンマ−アルミナを支持体として使用し、酢酸セリウム及び硝酸ジルコニウムを、Zr/Ce重量比が0.75となるように支持体に含浸させ、かつCe−Zrの重量がアルミナ支持体に対し5重量%となるように担持させてから乾燥させ、さらに900℃で6時間焼成してCe−Zr/γ−Al2O3支持体を製造した。前記Ce−Zr/γ−Al2O3支持体に対し、ニッケル前駆体として硝酸ニッケル六水和物(Ni(NO3)2・6H2O)を12重量%となるように担持させ、真空乾燥機中70℃で12時間撹拌して溶媒である水を除去し、100℃のオーブンで24時間以上乾燥させた後、900℃で6時間焼成して最終触媒であるNi/Ce−Zr/γ−Al2O3を製造した。このとき、触媒の比表面積は110m2/g、気孔体積は0.34cm3(cc)/g、平均気孔サイズは14.1nmであった。
Claims (11)
- MgO/Al2O3の重量比が3/7〜7/3であるMgAlOxに、Ce単独又はCeとZrとの混合物が前記MgAlOxの重量対比3〜20重量%の範囲で含まれているCe/MgAlOx又はCe−Zr/MgAlOxを支持体とし、
前記支持体に対し、活性成分としてNiを5〜20重量%となるように担持させた後、600〜1000℃で焼成することにより得られた、比表面積が80〜200m2/gであり、天然ガスの水蒸気改質反応及び二酸化炭素改質反応を同時に進行させるために使用される混合型改質反応用触媒。 - メタノール合成反応又はフィッシャー・トロプシュ反応のための合成ガスの製造に使用されることを特徴とする、請求項1記載の混合型改質反応用触媒。
- 天然ガスの水蒸気改質反応及び二酸化炭素改質反応を同時に進行させるために使用される混合型改質反応用触媒の製造方法であって、
1)MgO/Al2O3の重量比が3/7〜7/3であるMgAlOx支持体上に担持させたCe又はCe−Zrを、前記MgAlO x 支持体の重量に対する含有量が3〜20重量%ならびにCe及びZrの金属の重量組成比(Zr/Ce)が0〜4の範囲を維持するように、600〜900℃で焼成してCe(Zr)/MgAlOx混合型改質用支持体を製造するステップと、
2)Ce/MgAlOx支持体又はCe−Zr/MgAlOx支持体に対し5〜20重量%となるように、活性成分としてNiを前記支持体に担持させた後、600〜1000℃で焼成して触媒を製造するステップと
を含むことを特徴とする方法。 - 前記MgAlOx支持体は、アルミナ前駆体及びマグネシウム前駆体の金属の混合物に塩基性沈殿剤を加え、塩基性水溶液中で共沈させることにより製造されることを特徴とする、請求項3記載の方法。
- 前記アルミナ前駆体又はマグネシウム前駆体は、酢酸塩、水酸化塩又は硝酸塩であることを特徴とする、請求項4記載の方法。
- 前記塩基性沈殿剤は、炭酸ナトリウム(Na2CO3)、炭酸カリウム(K2CO3)、炭酸アンモニウム((NH4)2CO3)又は炭酸水素ナトリウム(NaHCO3)であることを特徴とする、請求項4記載の方法。
- 天然ガスの水蒸気改質反応及び二酸化炭素改質反応を同時に進行させるために使用される混合型改質反応用触媒の製造方法であって、MgO/Al2O3の重量比が3/7〜7/3であるMgAlOx支持体上に、金属前駆体であるNiとともにCe又はCe−Zrを、MgAlOx支持体の重量に対しCe又はCe−Zrが3〜20重量%、Ce/MgAlO x 支持体又はCe−Zr/MgAlO x 支持体の重量に対しNiが5〜20重量%となるように同時に担持させた後、600〜1000℃で焼成して触媒を製造することを特徴とする方法。
- 前記金属前駆体は、酢酸塩、水酸化塩及び硝酸塩から選択される1種以上であることを特徴とする、請求項7記載の方法。
- 合成ガスの製造方法であって、
請求項1又は請求項2記載の触媒を700〜1000℃で水素気体により還元処理して得られた触媒上において、反応温度800〜1000℃、反応圧力50.7〜2026kPa(0.5〜20気圧)、空間速度1,000〜500,000h−1、CH4/H2O/CO2のモル比1/1.0〜2.0/0.3〜0.6の条件下で、天然ガスの水蒸気改質反応及び二酸化炭素改質反応を同時に進行させる混合型改質反応を実施することを特徴とする方法。 - 前記混合型改質反応において、CH4の転換率が80%以上かつCO2の転換率が45%以上に維持され、かつH2/(2CO+3CO2)のモル比が0.85〜1.15に維持されることを特徴とする、請求項9記載の方法。
- 前記混合型改質反応の前記条件下において、H2/(2CO+3CO2)のモル比の変化率が2%未満であることを特徴とする、請求項9記載の方法。
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KR1020080075787A KR100991263B1 (ko) | 2008-08-01 | 2008-08-01 | 천연가스를 수증기와 이산화탄소로 동시에 개질하는 혼합개질 반응용 니켈계 촉매 |
PCT/KR2009/004256 WO2010013958A2 (ko) | 2008-08-01 | 2009-07-30 | 천연가스와 이산화탄소로부터 합성가스 제조를 위한 촉매 및 이의 제조방법 |
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Families Citing this family (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101068995B1 (ko) | 2008-12-08 | 2011-09-30 | 현대중공업 주식회사 | 메탄, 수증기 및 이산화탄소를 혼합 개질반응하여 생성된 합성가스를 이용한 메탄올의 합성방법 |
US8486301B2 (en) * | 2009-04-13 | 2013-07-16 | U.S. Department Of Energy | Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream |
KR101432621B1 (ko) * | 2011-09-08 | 2014-08-21 | 한국에너지기술연구원 | 합성가스 제조용 개질 촉매, 이를 이용한 합성가스 제조 방법 및 합성가스 제조 반응기 |
JP6125518B2 (ja) * | 2011-11-08 | 2017-05-10 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | メタン化触媒を製造するための方法および合成ガスのメタン化のための方法 |
US9259712B2 (en) | 2011-11-08 | 2016-02-16 | Basf Se | Process for producing a reforming catalyst and the reforming of methane |
WO2013068905A1 (en) * | 2011-11-08 | 2013-05-16 | Basf Se | Process for producing reforming catalyst and reforming of methane |
US8916491B2 (en) | 2011-11-08 | 2014-12-23 | Basf Se | Process for producing a methanation catalyst and a process for the methanation of synthesis gas |
KR101359992B1 (ko) * | 2011-12-28 | 2014-02-12 | 재단법인 포항산업과학연구원 | 메탄 개질 촉매 및 이의 제조방법 |
KR101964767B1 (ko) * | 2012-08-06 | 2019-04-02 | 연세대학교 원주산학협력단 | 합성가스의 제조 방법 및 액체 연료의 제조방법 |
ES2807356T3 (es) * | 2012-09-25 | 2021-02-22 | Haldor Topsoe As | Catalizador de reformado con vapor y procedimiento para fabricar el mismo |
KR101421825B1 (ko) * | 2012-12-12 | 2014-07-22 | 한국가스공사 | 수증기-이산화탄소 개질에 의한 합성가스 제조용 촉매 및 이를 이용한 합성가스 제조방법 |
WO2014104756A1 (ko) * | 2012-12-27 | 2014-07-03 | 재단법인 포항산업과학연구원 | 철광석 환원을 위한 환원 가스 제조용 니켈계 개질 촉매 및 그 제조방법, 에너지 효율을 극대화한 개질촉매 반응 공정 및 설비, 그리고, 이를 이용한 환원가스 제조방법 |
KR101467169B1 (ko) * | 2013-02-27 | 2014-12-01 | 한국화학연구원 | 메탄의 혼합 개질 반응용 니켈-함유 촉매성형체의 제조방법 및 수득된 촉매성형체 |
US9757714B2 (en) | 2013-02-27 | 2017-09-12 | Haldor Topsoe A/S | Methanation process using stabilized catalyst support comprising transition alumina |
KR20140122117A (ko) | 2013-04-09 | 2014-10-17 | 삼성전자주식회사 | 탄화수소의 이산화탄소 개질용 촉매 |
KR101465776B1 (ko) | 2013-05-16 | 2014-12-01 | 한국과학기술연구원 | 혼합 개질 반응에 사용되는 알칼리 토금속이 공침된 니켈계 촉매 |
KR101405517B1 (ko) | 2013-05-22 | 2014-06-11 | 한국과학기술연구원 | 혼합 개질 반응에 이용되는 니켈계 촉매의 제조방법 |
KR101469455B1 (ko) * | 2013-05-29 | 2014-12-22 | 한국화학연구원 | 합성가스 제조용 나노복합체 촉매, 이의 제조방법 및 이를 이용한 합성가스 제조방법 |
JP6229508B2 (ja) * | 2014-01-21 | 2017-11-15 | 株式会社Ihi | 酸素燃焼ボイラシステム |
JP6197052B2 (ja) * | 2014-02-05 | 2017-09-13 | 三井金属鉱業株式会社 | 燃料改質触媒 |
JP6308811B2 (ja) * | 2014-03-03 | 2018-04-11 | 昭栄化学工業株式会社 | 炭化水素リフォーミング用触媒及び合成ガスの製造方法 |
CN103816913B (zh) * | 2014-03-06 | 2016-03-30 | 太原理工大学 | 一种甲烷二氧化碳重整制合成气的催化剂及其制备方法和应用 |
WO2016011240A1 (en) | 2014-07-17 | 2016-01-21 | Sabic Global Technologies B.V. | Use of olivine catalysts for carbon dioxide reforming of methane |
KR101790102B1 (ko) | 2014-08-04 | 2017-10-25 | 한국화학연구원 | 이산화탄소의 배출을 저감시킬 수 있는 고효율 메탄올 생산 방법 |
CN104258864A (zh) * | 2014-09-03 | 2015-01-07 | 中国科学院上海高等研究院 | 纳米复合物催化剂及其制备方法与应用 |
CN104383927B (zh) * | 2014-11-17 | 2016-06-01 | 太原理工大学 | 一种甲烷与二氧化碳重整制合成气的催化剂及其制备方法 |
US10478808B2 (en) * | 2015-07-01 | 2019-11-19 | Sabic Global Technologies B.V. | Synthesis of oxygen-mobility enhanced CeO2 and use thereof |
CN106944082B (zh) * | 2016-01-07 | 2019-07-12 | 中国石油化工股份有限公司 | 一种用于甲烷二氧化碳重整制合成气催化剂的制备方法 |
CN105709754A (zh) * | 2016-01-22 | 2016-06-29 | 张川川 | 一种用于co2和ch4重整合成气的催化剂及其制备方法 |
CN105642327A (zh) * | 2016-01-22 | 2016-06-08 | 张川川 | 一种用于甲烷生产合成气的重整催化剂及其制备方法 |
JP6828877B2 (ja) * | 2016-08-29 | 2021-02-10 | 国立大学法人九州大学 | ペーパー状触媒およびその製造方法、ペーパー状触媒配列体並びに炭化水素の改質方法 |
RU2638534C1 (ru) | 2016-12-15 | 2017-12-14 | Публичное акционерное общество "Нефтяная компания "Роснефть" | Катализатор конверсии природного или попутного газа в синтез-газ в процессе автотермического риформинга и способ его получения |
WO2019050335A1 (ko) * | 2017-09-07 | 2019-03-14 | 한국화학연구원 | 니켈계 촉매 및 이를 이용한 합성가스 제조 시스템 |
KR102212842B1 (ko) * | 2017-09-07 | 2021-02-05 | 한국화학연구원 | 알칼리 처리된 니켈계 촉매 및 이의 제조방법 |
US10906808B2 (en) | 2017-11-15 | 2021-02-02 | Gas Technology Institute | Noble metal catalysts and processes for reforming of methane and other hydrocarbons |
US10738247B2 (en) | 2017-11-15 | 2020-08-11 | Gas Technology Institute | Processes and systems for reforming of methane and light hydrocarbons to liquid hydrocarbon fuels |
AU2017440226B2 (en) * | 2017-11-15 | 2024-02-08 | Gas Technology Institute | Noble metal catalysts and processes for reforming of methane and other hydrocarbons |
US20190233734A1 (en) * | 2018-01-26 | 2019-08-01 | Greyrock Energy, Inc. | Micro-scale process for the direct production of liquid fuels from gaseous hydrocarbon resources |
US11111142B2 (en) | 2018-09-18 | 2021-09-07 | Gas Technology Institute | Processes and catalysts for reforming of impure methane-containing feeds |
JP7180256B2 (ja) * | 2018-10-01 | 2022-11-30 | 日本製鉄株式会社 | 水素製造用触媒成型物及び水素製造用触媒成型物の製造方法 |
CN109499578A (zh) * | 2019-01-23 | 2019-03-22 | 华东师范大学 | 一种Ni基催化剂及其制备方法和在以焦炉煤气为原料制备甲醇合成气中的应用 |
CN109590011A (zh) * | 2019-01-23 | 2019-04-09 | 华东师范大学 | 一种Ni基催化剂及其制备方法和在以煤制油尾气为原料制备合成气中的应用 |
CN110676472A (zh) * | 2019-09-30 | 2020-01-10 | 潍柴动力股份有限公司 | 一种固体氧化物燃料电池系统用燃料预处理催化剂及其制备方法 |
KR20220052099A (ko) | 2020-10-20 | 2022-04-27 | 한국화학연구원 | 메탄의 수증기 개질용 니켈계 촉매 및 이를 이용한 메탄의 수증기 개질 반응 |
CN112844397B (zh) * | 2021-01-22 | 2023-02-10 | 成都理工大学 | 一种用于乙酸自热重整制氢的铈钐固溶体镍基催化剂 |
CN112897463B (zh) * | 2021-04-21 | 2022-12-20 | 山东大学 | 一种电催化甲烷-二氧化碳制合成气的装置与方法 |
CN113499763A (zh) * | 2021-06-15 | 2021-10-15 | 中石化南京化工研究院有限公司 | 一种焦炉气等温甲烷化催化剂及其制备方法 |
CN113522293A (zh) * | 2021-07-06 | 2021-10-22 | 中国科学院广州能源研究所 | 一种甲烷二氧化碳干重整制氢催化剂的制备方法和应用 |
CN113772628A (zh) * | 2021-08-13 | 2021-12-10 | 中国石油大学(北京) | 一种利用沼气制取氢气的方法 |
US20230150823A1 (en) * | 2021-11-16 | 2023-05-18 | Dennis Schuetzle | CO2 hydrogenation catalysts for the commercial production of syngas |
CN114394574B (zh) * | 2021-12-16 | 2023-02-21 | 山东能源集团有限公司 | 一种低温等离子体催化二氧化碳与甲烷混合气制备液体产物的方法 |
CN115180593B (zh) * | 2022-06-17 | 2024-01-19 | 北京化工大学 | 一种光驱动的碳酸盐炼制共热耦合烃类重整制高附加值产品的方法 |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3272205D1 (en) * | 1981-12-21 | 1986-08-28 | Ici Plc | Process for steam reforming a hydrocarbon feedstock and catalyst therefor |
US5039510A (en) * | 1983-03-25 | 1991-08-13 | Imperial Chemical Industries Plc | Steam reforming |
US5118715A (en) * | 1983-12-20 | 1992-06-02 | Exxon Research And Engineering Company | Selective fixed-bed fischer-tropsch synthesis with high surface area Cu and K promoted, iron/manganese spinels |
GB8728882D0 (en) * | 1987-12-10 | 1988-01-27 | Ici Plc | Hydrogen |
US5980840A (en) * | 1997-04-25 | 1999-11-09 | Bp Amoco Corporation | Autothermic reactor and process using oxygen ion--conducting dense ceramic membrane |
US6348278B1 (en) * | 1998-06-09 | 2002-02-19 | Mobil Oil Corporation | Method and system for supplying hydrogen for use in fuel cells |
EP1013603A1 (en) * | 1998-12-22 | 2000-06-28 | Haldor Topsoe A/S | Process for catalytical steam reforming of a hydrocarbon feedstock |
CN1093433C (zh) * | 1999-02-10 | 2002-10-30 | 石油大学(北京) | 天然气自热氧化重整制合成气催化剂及其制备方法 |
JP4355047B2 (ja) * | 1999-04-05 | 2009-10-28 | 石油資源開発株式会社 | リホーミング用触媒およびこれを用いた合成ガスの製法 |
US6497856B1 (en) * | 2000-08-21 | 2002-12-24 | H2Gen Innovations, Inc. | System for hydrogen generation through steam reforming of hydrocarbons and integrated chemical reactor for hydrogen production from hydrocarbons |
KR100394076B1 (ko) | 2000-09-16 | 2003-08-09 | 주식회사 경동도시가스 | 합성가스 제조용 니켈계 개질촉매 및 이를 이용하는수증기 개질에 의한 천연가스로부터 합성가스의 제조방법 |
KR100390774B1 (ko) | 2000-09-30 | 2003-07-10 | 한국화학연구원 | 산소개질 또는 수증기-산소 혼합개질에 의한천연가스로부터 합성가스의 제조방법 |
KR20020027121A (ko) | 2000-10-06 | 2002-04-13 | 박용호 | 물전기분해식 연료 발생장치 |
KR100825157B1 (ko) * | 2000-11-08 | 2008-04-24 | 이데미쓰 고산 가부시키가이샤 | 탄화수소의 개질 촉매 및 이를 사용하는 탄화수소의 개질방법 |
MXPA03004997A (es) * | 2000-12-05 | 2003-09-05 | Texaco Development Corp | Aparato y metodo para calentamiento de catalizador para inicio de operacion de procesador de combustible compacto. |
KR100398058B1 (ko) | 2001-05-18 | 2003-09-19 | 주식회사 경동도시가스 | 수식된 θ-알루미나에 담지되어 이루어진 니켈계 개질촉매및 이를 이용한 천연가스로부터 합성가스의 제조방법 |
JP2004066170A (ja) * | 2002-08-08 | 2004-03-04 | Nissan Motor Co Ltd | モノリス型燃料改質触媒とその製法 |
JP4316323B2 (ja) * | 2002-10-04 | 2009-08-19 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素リフォーミング用触媒及びその製造方法 |
US20050265920A1 (en) * | 2002-11-11 | 2005-12-01 | Conocophillips Company | Supports and catalysts comprising rare earth aluminates, and their use in partial oxidation |
KR100482646B1 (ko) | 2002-12-13 | 2005-04-14 | 한국화학연구원 | 공침법으로 제조된 천연가스 개질반응용 촉매 |
KR100553701B1 (ko) | 2003-11-28 | 2006-02-24 | (주)에너피아 | 합성 가스 제조를 위한 고활성 촉매, 이의 제조방법 및이를 이용한 합성가스의 제조공정 |
CN1921937B (zh) * | 2004-02-19 | 2011-07-27 | 出光兴产株式会社 | 烃的重整催化剂、利用该重整催化剂生产氢的方法以及燃料电池系统 |
KR100622027B1 (ko) | 2004-08-11 | 2006-09-28 | 한국화학연구원 | 고분산 귀금속 담지 혼합 금속산화물 탈질촉매 및 이의제조방법 |
JP4332733B2 (ja) * | 2004-08-24 | 2009-09-16 | 戸田工業株式会社 | 炭化水素分解用触媒及び該炭化水素分解用触媒を用いた水素の製造方法 |
KR100711349B1 (ko) | 2005-06-17 | 2007-04-27 | 한국가스공사 | 삼중개질반응을 이용한 합성가스의 제조방법 |
KR101319137B1 (ko) * | 2005-08-11 | 2013-10-17 | 도다 고교 가부시끼가이샤 | 탄화수소를 분해하는 촉매, 상기 촉매를 이용한 탄화수소의분해 방법 및 수소의 제조 방법, 및 발전 시스템 |
KR101300501B1 (ko) | 2005-10-20 | 2013-08-26 | 에스케이이노베이션 주식회사 | 유사 하이드로탈사이트 전구체를 이용한 니켈계 촉매와이를 이용한 액화석유가스의 수증기 개질반응 |
US20070167323A1 (en) * | 2006-01-16 | 2007-07-19 | Toda Kogya Corporation | Porous carrier for steam-reforming catalysts, steam-reforming catalyst and process for producing reactive mixed gas |
KR100723392B1 (ko) | 2006-02-02 | 2007-05-30 | 삼성에스디아이 주식회사 | 복합 산화물 담지체, 저온 쉬프트 반응 촉매 및 그의 제조방법 |
US8142756B1 (en) * | 2006-03-28 | 2012-03-27 | The United States Of America As Represented By The U.S. Department Of Energy | Methods of reforming hydrocarbon fuels using hexaaluminate catalysts |
KR20080072286A (ko) | 2007-02-01 | 2008-08-06 | 주식회사 키스컴 | 고유전율 유전체 및 그 제조방법, 이를 이용한 칩형 안테나 |
CN101049566A (zh) * | 2007-05-23 | 2007-10-10 | 天津大学 | 用于甲烷部分氧化制合成气的Ni基催化剂及其制备方法 |
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AU2009277275B2 (en) | 2012-12-13 |
US8524119B2 (en) | 2013-09-03 |
CN102112227B (zh) | 2015-05-20 |
EP2308594A4 (en) | 2012-11-21 |
WO2010013958A3 (ko) | 2010-06-10 |
KR100991263B1 (ko) | 2010-11-01 |
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