JP2010501529A - 水素リッチなオレフィン含有気体混合物から酸素、酸化窒素、アセチレン及び/又はジエンを除去する方法 - Google Patents
水素リッチなオレフィン含有気体混合物から酸素、酸化窒素、アセチレン及び/又はジエンを除去する方法 Download PDFInfo
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- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
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Abstract
【選択図】なし
Description
酸化銅を含む触媒(45%のCuO、16%のMgO、35%のSiO2、0.9%のCr2O3、1.1%のBaO及び0.6%のZnO)から開始して、酸化物の銅を、第1の工程において、水素含有雰囲気での還元によって単体の銅に転化した。この場合、50mlの、酸化物の形の酸化銅触媒を200mlの反応器に導入した。反応器を不活性にし、そして水素含有気体を、大気圧下で反応器に通過させた(100標準L/時、N2における5%のH2、200℃、24時間)。かかる還元の後、触媒を硫化に付した。この場合、1体積%の、H2におけるH2S(合計して50標準L/時)を、10バール及び220℃の条件下で還元された触媒に6時間に亘って通過させた。このようにして得られた硫化された銅触媒を、次に分析した。XRDでは、単体の銅クリスタライトをもはや検出しなかった;むしろ、XRDでは、Cu2S及び少量のCu31S16を検出した。元素分析では、3.78のCu/S質量比を示していた。1.8:1〜2.4:1の元素比を、流化の条件に応じて得ることが可能であった。
また、水素で還元された銅触媒を、液相中のポリスルフィドと反応させることによって、触媒を良好に製造することが可能であった。この場合、例えば、200gの還元された銅触媒を、35gのジ−tert−ブチルポリスルフィドを200gのヘプタンに溶解させた溶液に添加した。次に、溶剤を減圧下に50℃の条件下で蒸留した。次に、触媒を50℃及び10ミリバールの条件下で乾燥した。
PuriStar R3-81、すなわち銅含有触媒は、実施例1に記載の方法によって得ることが可能であったが、CuO含有前駆体を、水素含有気体によってその場で最初に活性化し、次に、水素中でH2Sによって硫化された形に転化した。
試験は、連続運転される実験用反応器(50mlの触媒)において行われた。個々の気体の開始成分を混合し、次に、反応温度まで予備加熱した後に、反応器に入り込んだ。反応混合物は、頂部から下方に向かって、補助的加熱器を具備した断熱反応器を通過して流れた。反応温度を150〜250℃の範囲で変化させた。反応器の圧力は、10バールであった。温度は、触媒床に沿って設けられた複数の熱電対によって測定された。実施例3の触媒をペレットの形で使用した。反応器に通過させた後、生成物の気体混合物を、大気圧まで減圧した。生成物の気体混合物における炭化水素成分を、GCによってオンライン分析した。O2濃度についても同様にオンライン分析した。開始気体混合物は、以下の組成を有していた(MAPD=メチルアセチレン/プロパジエン):
MAPD: 20ppm
1,3−ブタジエン: 20ppm
1−ブテン: 1体積%
H2S: 20ppm
O2: 200ppm
NOx: 250ppm
CO: 3体積%
H2: 20体積%
C2H4: 13体積%
C3H6: 5体積%
Hg: 10ppm
As: 10ppm
エタン: 0.002%
プロパン: 0.002%
メタン: バランス。
Claims (15)
- 酸素、酸化窒素、アセチレン及びジエンからなる群から選択される少なくとも1種の成分と、更には水素と、ジエンではない1種以上のオレフィンと、必要により他の気体成分とを含む気体混合物から少なくとも1種の成分を除去する方法であって、
気体混合物を、反応領域において、硫化銅(I)を含む触媒と接触させることを特徴とする除去方法。 - 触媒が、硫化銅(I)を担体に含む請求項1に記載の方法。
- 気体混合物が酸素を含む請求項1に記載の方法。
- 気体混合物が酸化窒素を含む請求項1に記載の方法。
- 気体混合物がアセチレンを含む請求項1に記載の方法。
- 気体混合物がジエンを含む請求項1に記載の方法。
- 気体混合物がオレフィンとしてエテン及び/又はプロペンを含む請求項1に記載の方法。
- 供給材料の気体混合物における酸素含有量が、1ppm〜3体積%の範囲である請求項1に記載の方法。
- 供給材料の気体混合物における酸化窒素含有量が、1〜2000ppmの範囲である請求項1に記載の方法。
- 供給材料の気体混合物におけるアセチレン含有量が、5ppm〜1体積%の範囲である請求項1に記載の方法。
- 供給材料の気体混合物におけるジエン含有量が、5ppm〜1体積%の範囲である請求項1に記載の方法。
- 気体混合物における水素含有量が、1〜70体積%の範囲である請求項1に記載の方法。
- 供給材料の気体混合物におけるオレフィン含有量が、1〜60体積%の範囲である請求項1に記載の方法。
- 反応領域における温度が150〜300℃の範囲であり、そして反応領域における圧力が5〜40バールの範囲である請求項1に記載の方法。
- 供給材料の気体混合物が、リン、ヒ素、カドミウム、水銀、バナジウム及び/又は鉛を含む1種以上の化合物を含み、且つこれらの化合物は、触媒への吸着によって気体混合物から除去される請求項1に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US84002606P | 2006-08-25 | 2006-08-25 | |
US60/840,026 | 2006-08-25 | ||
PCT/EP2007/058792 WO2008023051A1 (de) | 2006-08-25 | 2007-08-24 | Verfahren zur entfernung von sauerstoff, stickstoffoxiden, acetylenen und/oder dienen aus wasserstoffreichen olefinhaltigen gasgemischen |
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JP2010501529A true JP2010501529A (ja) | 2010-01-21 |
JP5591537B2 JP5591537B2 (ja) | 2014-09-17 |
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JP2009525074A Expired - Fee Related JP5591537B2 (ja) | 2006-08-25 | 2007-08-24 | 水素リッチなオレフィン含有気体混合物から酸素、酸化窒素、アセチレン及び/又はジエンを除去する方法 |
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US (1) | US8586815B2 (ja) |
EP (1) | EP2056962B1 (ja) |
JP (1) | JP5591537B2 (ja) |
KR (1) | KR101452529B1 (ja) |
CN (1) | CN101505866B (ja) |
BR (1) | BRPI0715798B1 (ja) |
CA (1) | CA2660334C (ja) |
ES (1) | ES2564558T3 (ja) |
HU (1) | HUE029626T2 (ja) |
TW (1) | TWI414516B (ja) |
WO (1) | WO2008023051A1 (ja) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
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AR067902A1 (es) * | 2007-08-17 | 2009-10-28 | Shell Int Research | Un proceso para remover azufre de una corriente de gas combustible que adicionalmente contiene diolefinas y oxigeno |
US8969240B2 (en) * | 2008-11-25 | 2015-03-03 | Johnson Matthey Plc | Reduced copper sulphide sorbent for removing heavy metals |
GB0905896D0 (en) | 2009-04-06 | 2009-05-20 | Univ Belfast | Process for removing metals from hydrocarbons |
SG10201402228SA (en) | 2009-05-12 | 2014-07-30 | Basf Se | Process for producing propylene oxide |
JP5300643B2 (ja) * | 2009-07-28 | 2013-09-25 | Jx日鉱日石エネルギー株式会社 | 気体状の炭化水素中の窒素酸化物の測定方法 |
ES2613947T3 (es) * | 2009-12-15 | 2017-05-29 | Uop Llc | Eliminación de mercurio de un gas de craqueo |
KR101621601B1 (ko) * | 2010-12-20 | 2016-05-16 | 유오피 엘엘씨 | 점토를 사용하여 탄화수소 스트림으로부터 불포화 지방족 탄화수소를 제거하는 방법 |
US9670115B2 (en) | 2012-02-15 | 2017-06-06 | Clariant Corporation | Method and system for purifying an ethylene-containing gas stream |
CN104395269A (zh) * | 2012-06-29 | 2015-03-04 | 赫多特普索化工设备公司 | 通过加氢净化原料气 |
US8609048B1 (en) * | 2012-11-02 | 2013-12-17 | Uop Llc | Process for reducing corrosion, fouling, solvent degradation, or zeolite degradation in a process unit |
CN104797693A (zh) * | 2012-11-15 | 2015-07-22 | 埃克森美孚化学专利公司 | NOx除去方法 |
WO2017083116A1 (en) | 2015-11-10 | 2017-05-18 | Uop Llc | Copper adsorbent for gas purification |
EP3374059A4 (en) * | 2015-11-10 | 2019-05-22 | Uop Llc | COPPER ADSORBENT FOR ACETYLENE CONVERTER PROTECTION BED |
EP3752587A4 (en) | 2018-02-12 | 2021-11-24 | Lanzatech, Inc. | INTEGRATED PROCESS FOR FILTERING CONSTITUENTS FROM A GAS FLOW |
RU2760125C1 (ru) * | 2021-04-30 | 2021-11-22 | Общество с ограниченной ответственностью "Юнайтед Кэталист Текнолоджис" | Способ очистки углеводородных газов от N2O |
RU2760126C1 (ru) * | 2021-05-12 | 2021-11-22 | Общество с ограниченной ответственностью "Юнайтед Кэталист Текнолоджис" | Способ очистки потоков насыщенных углеводородов от примесей |
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JPS62132549A (ja) * | 1985-11-29 | 1987-06-15 | ウエスチングハウス エレクトリック コ−ポレ−ション | 無機重合体カチオン交換母材 |
JPS62145032A (ja) * | 1985-11-27 | 1987-06-29 | ザ ブリテイツシユ ペトロレアム カンパニ− ピ−.エル.シ− | アセチレンの選択的水素化によるエチレンの製造方法 |
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JP2006502211A (ja) * | 2002-10-08 | 2006-01-19 | ビーピー ケミカルズ リミテッド | オレフィン含有プロセス流からの酸素の除去方法 |
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US3456029A (en) * | 1966-07-20 | 1969-07-15 | Yawata Chem Ind Co Ltd | Process for the purification of lower olefin gases |
JPS5062856A (ja) * | 1973-09-13 | 1975-05-29 | ||
FR2668465B1 (fr) * | 1990-10-30 | 1993-04-16 | Inst Francais Du Petrole | Procede d'elimination de mercure ou d'arsenic dans un fluide en presence d'une masse de captation de mercure et/ou d'arsenic. |
GB9607066D0 (en) * | 1996-04-03 | 1996-06-05 | Ici Plc | Purification process |
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- 2007-08-24 US US12/438,436 patent/US8586815B2/en active Active
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS62145032A (ja) * | 1985-11-27 | 1987-06-29 | ザ ブリテイツシユ ペトロレアム カンパニ− ピ−.エル.シ− | アセチレンの選択的水素化によるエチレンの製造方法 |
JPS62132549A (ja) * | 1985-11-29 | 1987-06-15 | ウエスチングハウス エレクトリック コ−ポレ−ション | 無機重合体カチオン交換母材 |
US5689032A (en) * | 1994-11-22 | 1997-11-18 | Krause/Pasadyn, A Partnership | Method and apparatus for recovery of H2 and C2 and heavier components |
JP2006502211A (ja) * | 2002-10-08 | 2006-01-19 | ビーピー ケミカルズ リミテッド | オレフィン含有プロセス流からの酸素の除去方法 |
Also Published As
Publication number | Publication date |
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ES2564558T3 (es) | 2016-03-23 |
CN101505866A (zh) | 2009-08-12 |
CA2660334A1 (en) | 2008-02-28 |
KR101452529B1 (ko) | 2014-10-21 |
CA2660334C (en) | 2014-07-15 |
TW200815340A (en) | 2008-04-01 |
KR20090053799A (ko) | 2009-05-27 |
JP5591537B2 (ja) | 2014-09-17 |
WO2008023051A1 (de) | 2008-02-28 |
US20100000911A1 (en) | 2010-01-07 |
EP2056962B1 (de) | 2016-01-27 |
HUE029626T2 (en) | 2017-03-28 |
EP2056962A1 (de) | 2009-05-13 |
US8586815B2 (en) | 2013-11-19 |
CN101505866B (zh) | 2013-05-15 |
BRPI0715798B1 (pt) | 2016-12-06 |
BRPI0715798A2 (pt) | 2013-07-16 |
TWI414516B (zh) | 2013-11-11 |
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