JP4653108B2 - 尿素の製造方法 - Google Patents
尿素の製造方法 Download PDFInfo
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- JP4653108B2 JP4653108B2 JP2006538796A JP2006538796A JP4653108B2 JP 4653108 B2 JP4653108 B2 JP 4653108B2 JP 2006538796 A JP2006538796 A JP 2006538796A JP 2006538796 A JP2006538796 A JP 2006538796A JP 4653108 B2 JP4653108 B2 JP 4653108B2
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims description 21
- 239000004202 carbamide Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 234
- 239000003054 catalyst Substances 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 238000001651 catalytic steam reforming of methanol Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 36
- 239000001257 hydrogen Substances 0.000 description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000446 fuel Substances 0.000 description 8
- 238000000629 steam reforming Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229940095895 haldol Drugs 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/04—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from carbon dioxide and ammonia
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/10—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds combined with the synthesis of ammonia
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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Description
CO + H2O → CO2 + H2 (1)
これは、より多くの水素の製造に使用される僅かに発熱性の反応である。工業的な高温シフト(HTS)の用途における公知のWGS触媒は、クロムに担持された鉄に基づく高温触媒であり、そしてこれらは、時折、促進剤として銅を含む。このHTSの操業範囲は典型的には340〜360℃の入口温度及び約100℃以上の出口温度である。低温シフト(LTS)触媒のための入口温度の操業範囲は200℃以上(またはガスの露点よりも20℃高い温度)である。入口温度はできる限り低く抑えるべきである。シフト反応用触媒及び操業温度についての更なる詳細は、Catalyst Handbook,第二版,Manson Publishing Ltd.England 1996に記載されている。
CH3OH + H2O → 3H2 + CO2 (2)
の吸熱性メタノール水蒸気改質反応は、ガス中の顕熱から並びにWGS反応からの潜熱から必要な反応熱を得る。本発明の方法で利用される触媒は、最大入口温度に耐え、そして出口メタノール濃度をできる限り低く抑える必要から主に決定されるかなりより低い温度(典型的には240〜320℃の温度範囲)においてもなお活性を示す。
CH3OH + H2O→ 3H2 + CO2 (2)
3H2 + N2 → 2NH3 (3)
2NH3 + CO2 → (NH2)2CO + H2O (4)
軽質天然ガスの水蒸気改質から生じる合成ガスは、CO2が不足している。多量のメタノールを加えることで、主改質器における加熱は不要になる。すなわち加熱は余分である。この工程(反応(2))で生成する二酸化炭素は、追加の尿素製造(反応(3及び4))のためにアンモニアプラントに使用することができる。本発明の方法では、尿素は、慣用の方法を用いて反応(4)に従いアンモニア及び二酸化炭素を反応させることによって製造される。それゆえ、メタノールを使用して、アンモニアプラントの燃料の柔軟性を高め、そしてこれと同時に尿素の製造のためにCO2を供給することができる。
触媒A: SK201−2: 銅、鉄及びクロムの各々の酸化物からなる高温シフト触媒
触媒B: MK101: 銅、亜鉛及びアルミニウムの各々の酸化物からなるメタノール合成触媒
触媒C: MK121: 銅、亜鉛及びアルミニウムの各々の酸化物からなるメタノール合成触媒
反応は全て、0〜10MPag、好ましくは2〜6MPagの圧力で行う。この圧力は、その表示通り大気圧を超えた分の値である。
触媒A 10gを、水蒸気と、CO15%、CO210%及びH275%を含む乾燥ガスとで活性化する。これを更に、50Nl/hの乾燥ガス流量及び45Nl/hの水蒸気流量で、2.3MPaの圧力下に380℃で試験する。70時間後、乾燥出口ガス中のCO濃度は3.7%である。更に、メタノール0.5Nl/hを加えると、CO出口濃度が4.0%に高まり、そして出口CH4濃度が20ppmから1000ppmに高まる。更に、反応器を出た後に凝縮した水は、添加したメタノールの約50%に相当する、かなりの量の未転化のメタノールを含んでいた。メタノールを除くと、CH4の生成が25ppmに減少し、COの生成は3.9%に減少した。
触媒B 15.2gを、希釈水素(1〜5体積%)中で、185℃及び0.1MPaの圧力下に還元し、そして水素43.1%、一酸化炭素14.3%、二酸化炭素11.1%及び窒素31.5%からなる合成ガスを導入する。圧力を2.5MPaに高め、そして温度を235℃に高める。水中19.63%wt/wtのメタノールの溶液を蒸発し、そして前記合成ガスと一緒に導入する。この乾燥ガス流量は100Nl/hであり、他方、液体流量は、41.6Nl/hの水蒸気流量及び5.7Nl/hのメタノール流量に相当する、41.6g/hである。出口ガスは、残留水蒸気及びメタノールの凝縮後に分析する。これらの条件の下に、CO出口濃度は0.90%に達し、そしてCO2出口濃度は21.7%であり、そして乾燥ガス流量は130Nl/hに高められる。約1ppmの検出限界において、どの時点においてもCH4は観察されない。
温度、乾燥ガス流量及び液体流量を表1に記載ように変えた以外は例2の通りに行う。触媒は、例2で使用したものと同じバッチである。例7の出口ガスの凝縮可能な部分を分析することにより、10ppm wt/wtのエタノール濃度が判明する。例3〜7のいずれにもより高級のアルコール、メタンまたは他のどのような炭化水素も観察されない。それゆえ、炭素酸化物類及び水素へのメタノール転化の選択性は、実験の精度内においては100%である。
15.1gの触媒Cを、乾燥希釈水素(1〜5体積%)中で、185℃及び0.1MPaの圧力の下に還元し、そして水素43.1%、一酸化炭素14.3%、二酸化炭素11.1%及び窒素31.5%からなる合成ガスを導入する。圧力を2.5MPaまで高め、そして温度を216℃に高める。水中22.37%のメタノールの溶液を蒸発させ、そして上記合成ガスと一緒に供給する。乾燥ガス流量は50Nl/hであり、他方、液体流量は、15.5Nl/hの水蒸気流量及び2.5Nl/hのメタノール流量に相当する16.0g/hである。残留水蒸気及びメタノールの凝縮後に出口ガスを分析する。これらの条件において、CO出口濃度は0.64%に達し、そしてCO2出口濃度は22.3%であり、そして乾燥流ガス流量は63Nl/hに高められる。約1ppmの検出限界において、いずれの時点でもCH4は観察されない。これらの条件において、出口温度は、触媒床の直ぐ後のところで219℃と測定され、そして反応器を出る液体流量は18.7g/hである(メタノール濃度は11.26%wt/wt)。それゆえ、メタノール出口流量は1.47Nl/hである。
この実験は、乾燥ガス流量及び液体流量を表2に示す通りに変える以外は例8と同様に行う。炭素酸化物類及び水素へのメタノール転化の選択性は100%である。
例8〜9に使用した触媒を、100Nl/hの乾燥ガス流量、60g/hの液体流量、2.5MPaの圧力で及び例8〜9と同じ供給組成物を用いて、313℃の入口温度で120分間、作用させる。炭素酸化物類及び水素へのメタノール転化の選択性は100%である。一酸化炭素の出口濃度は、この期間中、1.25±0.05%で一定している。120時間の期間の後に、凝縮物を再び分析した。その結果を表2に示す。
これらの実験は、温度、乾燥ガス流量及び液体流量を表2に示すように変える以外は例10と同様に行う。
これらの実験は、メタノールを液体供給物から除く以外は例10〜13と同様である。メタノールを加えない触媒Cの結果は表3に示す。
この例は、尿素の生産を高めるために、天然ガスに基づくアンモニアプラントにメタノールを加えることの利点を示すものである。
Claims (10)
- 一酸化炭素含有ガスにメタノールを加え、この一酸化炭素含有ガス、メタノール及び水を、銅、亜鉛及びアルミニウム及び/またはクロムを含む触媒の存在下に少なくとも一つのシフト段階において接触させて、二酸化炭素富化流を生じせしめ、上記二酸化炭素富化流を上記の少なくとも一つのシフト段階から尿素反応器に移し、そしてその二酸化炭素をアンモニアと反応させて、尿素を製造することを含み、この際、一酸化炭素含有ガスは、炭化水素供給物の改質及び/または部分酸化から得られるものである、尿素の製造方法。
- メタノール及び水が蒸気の形である、請求項1の方法。
- メタノール及び水が液体の形である、請求項1の方法。
- 少なくとも一つのシフト段階が、中温もしくは高温シフト段階である、請求項1及び2または3の方法。
- 中温もしくは高温シフト段階の次に低温シフト段階が続く、請求項4の方法。
- 炭化水素供給物が、改質段階の前に予備改質されている、請求項1の方法。
- 未反応メタノールを、シフト段階の流出流から分離し、そして予備改質段階に再循環する、請求項6の方法。
- シフト入口温度が少なくとも280℃であり、そして圧力が0〜10MPa g、好ましくは2〜6MPa gである、請求項4の方法。
- 少なくとも一つのシフト段階における一酸化炭素含有ガスとメタノール及び水との反応が、メタノール水蒸気改質と水性ガスシフト反応が同時に起こる条件下で行われる、請求項1〜8のいずれか一つの方法。
- 少なくとも一つのシフト段階における一酸化炭素含有ガスとメタノール及び水との反応が、6.0〜7.5の水蒸気/メタノールの流量比(NL/NL)で行われる、請求項1〜9のいずれか一つの方法。
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JPS59203702A (ja) * | 1983-05-04 | 1984-11-17 | Mitsubishi Heavy Ind Ltd | 水素の製造法 |
JPS6186946A (ja) * | 1984-10-05 | 1986-05-02 | Kawasaki Heavy Ind Ltd | メタノ−ル・スチ−ムリフオ−ミング用触媒 |
JPS61286203A (ja) * | 1985-06-14 | 1986-12-16 | Mitsubishi Heavy Ind Ltd | メタノ−ル改質方法 |
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US5523483A (en) * | 1995-06-16 | 1996-06-04 | The M. W. Kellogg Company | Integrated urea/ammonia process |
DE10010070A1 (de) * | 2000-03-02 | 2001-09-20 | Xcellsis Gmbh | Gaserzeugungsvorrichtung |
DE10055818A1 (de) * | 2000-11-10 | 2002-05-23 | Ammonia Casale Sa | Verfahren zum Herstellen von Ammoniak aus einem Stickstoff-Wasserstoff-Gemisch aus Erdgas |
US6448441B1 (en) * | 2001-05-07 | 2002-09-10 | Texaco, Inc. | Gasification process for ammonia/urea production |
ZA200507925B (en) * | 2003-04-01 | 2006-12-27 | Haldor Topsoe As | Process for the preparation of a hydrogen-rich stream |
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JPS59203702A (ja) * | 1983-05-04 | 1984-11-17 | Mitsubishi Heavy Ind Ltd | 水素の製造法 |
JPS6186946A (ja) * | 1984-10-05 | 1986-05-02 | Kawasaki Heavy Ind Ltd | メタノ−ル・スチ−ムリフオ−ミング用触媒 |
JPS61286203A (ja) * | 1985-06-14 | 1986-12-16 | Mitsubishi Heavy Ind Ltd | メタノ−ル改質方法 |
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CN100457724C (zh) | 2009-02-04 |
CA2546181C (en) | 2011-01-11 |
KR20060113712A (ko) | 2006-11-02 |
BRPI0406779A (pt) | 2006-01-17 |
BRPI0406779B1 (pt) | 2013-05-28 |
WO2005049554A1 (en) | 2005-06-02 |
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