[go: up one dir, main page]

CN101990517A - 制备合成气的方法ⅱ - Google Patents

制备合成气的方法ⅱ Download PDF

Info

Publication number
CN101990517A
CN101990517A CN2009801123006A CN200980112300A CN101990517A CN 101990517 A CN101990517 A CN 101990517A CN 2009801123006 A CN2009801123006 A CN 2009801123006A CN 200980112300 A CN200980112300 A CN 200980112300A CN 101990517 A CN101990517 A CN 101990517A
Authority
CN
China
Prior art keywords
hydrocarbon
oxygenated
drop
water vapour
nozzle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2009801123006A
Other languages
English (en)
Other versions
CN101990517B (zh
Inventor
S·多恩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gelato Corp NV
Original Assignee
Gelato Corp NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gelato Corp NV filed Critical Gelato Corp NV
Publication of CN101990517A publication Critical patent/CN101990517A/zh
Application granted granted Critical
Publication of CN101990517B publication Critical patent/CN101990517B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B3/32—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
    • C01B3/38—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 using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276—Mixing of different feed components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

本发明涉及一种制备合成气的方法，这包括以下步骤：a)制备一种含有水蒸气和至少一种烃或氧化烃的气相混合物，这通过用喷嘴将至少一种烃或氧化烃雾化进行，使得至少一种烃或氧化烃作为具有小于500微米液滴尺寸的液滴存在，并且完成蒸发的时间不超过0.5秒，所述至少一种烃或氧化烃具有在-50℃至370℃温度范围内的大气沸点，所述气相中的H2O/C摩尔比是至少2；和b)将气相混合物在重整器中催化转化成合成气。

Description

制备合成气的方法II
本发明涉及一种制备合成气的方法。
PCT/EP2007/007798公开了一种从烃或氧化烃制备合成气的方法，并随后从作为进料的烃或氧化烃单独地或与天然气一起开始制备甲醇或其它产品。在进入重整器之前制备烃或氧化烃的操作应当通过水蒸气蒸发进行。在此公开内容中，据说水蒸气(H2O)与碳之间的比率应当是按照摩尔计的至少2，优选至少2.5，最优选是3.2。
本发明涉及直接从经过传统提纯的烃或氧化烃制备合成气，优选从甘油制备。烃或氧化烃可以经由几种公知的路线获得，例如真空蒸馏或萃取，从例如来自植物油工业的粗甘油、动物脂肪、已用过的烹调油等开始。
如在现有技术中所述，水蒸气与碳之间的比率对于避免在管或管道中或在催化剂上形成碳是十分重要的。这里所选择的制备方法保持烃或氧化烃在蒸发期间被足够的水蒸气包围并且加热到进入重整器所需的温度。由于在例如甘油的常规提纯中不存在水蒸气，所以，技术人员将选择真空蒸馏，以此方式避免高温。
对于重整，需要10-20巴的压力，并且温度保持为约300-700℃。所以，通过真空蒸馏进行的提纯将不会是经济可行的技术方案，当必须加工大量时尤其如此。因为甘油在高于180℃的温度下快速地变差，所以在其暴露于高温期间的停留时间也将是非常重要的。
本发明的目的是提供一种代替现有技术的制备合成气的方法。此方法能容易实施，并且在蒸发路径需要较少设备方面是在经济上有吸引力的，因此将在投资中更加成本有效。惊奇的是，此目的可以通过一种制备合成气的方法实现，这包括以下步骤：
a)制备一种含有水蒸气和至少一种烃或氧化烃的气相混合物，这通过用喷嘴将至少一种烃或氧化烃雾化进行，使得至少一种烃或氧化烃作为具有小于500微米液滴尺寸的液滴存在，并且完成蒸发的时间不超过0.5秒，所述至少一种烃或氧化烃具有在-50℃至370℃温度范围内的大气沸点，所述气相中的H2O/C摩尔比是至少2，和
b)将气相混合物在重整器中催化转化成合成气。
优选，一种或多种氧化烃用做进料，甚至更优选氧化烃是甘油。
对于本发明方法，甘油可以是纯甘油或含有一些水和/或具有浅黄色/浅褐色的甘油作为进料。
气相混合物中的H2O/C摩尔比优选是2.5-4。
优选，气相混合物与天然气在其被催化转化成合成气之前混合。
液滴是通过用喷嘴将至少一种烃或氧化烃雾化而产生的，并且具有小于500微米的尺寸，优选小于200微米，最优选小于100微米。
优选，液滴是用雾化喷嘴产生的，这在水蒸气的辅助下进行。
甚至更优选，在喷嘴中的水蒸气与碳之间的比率是至少2.0，最优选将所有水蒸气经由喷嘴加入。
在本发明方法中，烃或氧化烃，例如甘油，是通过经由水蒸气支持的喷嘴的雾化组合来蒸发。将冷的或经过温和预热到低于180℃的烃或氧化烃，例如甘油，加入具有水蒸气室的喷嘴中，然后加入加热设备中。惊奇地发现，液滴尺寸不能超过500微米，优选不超过200微米，最优选不超过100微米，并且完成蒸发的时间应当不超过0.5秒，优选应当不超过0.3秒。如果选择液滴尺寸小于500微米和如果选择蒸发时间不超过0.5秒，则惊奇地发现烃或氧化烃(例如甘油)不会降解，且没有出现碳的形成。
但是，如果液滴尺寸超过500微米和如果蒸发时间超过0.5秒，则发现烃或氧化烃例如甘油发生降解，并且形成碳。
所有水蒸气与碳之间的比率将保持与现有技术中相同，例如PCT/EP2007/007798所述。所有水蒸气优选加入到所述雾化喷嘴中。如果尽管天然气与甘油一起加入重整器中，则水蒸气可以被分成两个料流，但是在喷嘴中的水蒸气与碳之间的比率应当是按摩尔计的至少2.0。在这些情况下，任何比率的甲烷和甘油可以加入重整器中。甘油也可以单独地加入。
所有其它条件、催化剂和设备与现有技术PCT/EP2007/007798所述相同，将其内容引入本文供参考。合成气主要是用于生产甲醇，但也适用于生产二甲醚(DME)、烯烃、烷烃、燃料产品等。

Claims (12)

1.一种制备合成气的方法，这包括以下步骤：
a)制备一种含有水蒸气和至少一种烃或氧化烃的气相混合物，这通过用喷嘴将至少一种烃或氧化烃雾化进行，使得至少一种烃或氧化烃作为具有小于500微米液滴尺寸的液滴存在，并且完成蒸发的时间不超过0.5秒，所述至少一种烃或氧化烃具有在-50℃至370℃温度范围内的大气沸点，所述气相中的H2O/C摩尔比是至少2，和
b)将气相混合物在重整器中催化转化成合成气。
2.权利要求1的方法，其中使用一种或多种氧化烃。
3.权利要求2的方法，其中氧化烃是甘油。
4.权利要求3的方法，其中甘油是纯甘油或含有一些水和/或具有浅黄色/浅褐色的甘油作为进料。
5.前述权利要求中任一项的方法，其中气相混合物中的H2O/C摩尔比是2.5-4。
6.前述权利要求中任一项的方法，其中气相混合物与天然气在其被催化转化成合成气之前混合。
7.前述权利要求中任一项的方法，其中液滴具有小于200微米的尺寸。
8.权利要求7的方法，其中液滴具有小于100微米的尺寸。
9.前述权利要求中任一项的方法，其中液滴是用雾化喷嘴产生的，这在水蒸气的辅助下进行。
10.权利要求9的方法，其中在喷嘴中的水蒸气与碳之间的比率是至少2.0。
11.权利要求10的方法，其中将所有水蒸气经由喷嘴加入。
12.前述权利要求中任一项的方法，其中合成气用于生产甲醇。
CN200980112300.6A 2008-03-10 2009-03-10 制备合成气的方法ii Active CN101990517B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08004336.7 2008-03-10
EP08004336A EP2103567A1 (en) 2008-03-10 2008-03-10 Process for the preparation of synthesis gas, II
PCT/EP2009/052760 WO2009112476A1 (en) 2008-03-10 2009-03-10 Process for the preparation of synthesis gas, ii

Publications (2)

Publication Number Publication Date
CN101990517A true CN101990517A (zh) 2011-03-23
CN101990517B CN101990517B (zh) 2014-05-21

Family

ID=39495116

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200980112300.6A Active CN101990517B (zh) 2008-03-10 2009-03-10 制备合成气的方法ii

Country Status (11)

Country Link
US (1) US8372310B2 (zh)
EP (2) EP2103567A1 (zh)
CN (1) CN101990517B (zh)
BR (1) BRPI0909327B1 (zh)
CO (1) CO6300857A2 (zh)
DK (1) DK2271583T3 (zh)
ES (1) ES2743411T3 (zh)
NZ (1) NZ588003A (zh)
RU (1) RU2494958C2 (zh)
WO (1) WO2009112476A1 (zh)
ZA (1) ZA201006669B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104702892A (zh) * 2013-12-09 2015-06-10 深圳市盛思维科技有限公司 基于Mesh网络的实时视频传输系统及其方法
CN105947979A (zh) * 2016-04-28 2016-09-21 中国科学院广州能源研究所 一种甲醇-甘油协同水蒸气重整制氢方法及用于该制氢方法的催化剂

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK2064149T3 (da) * 2006-09-08 2012-05-07 Gelato Corp N V Fremgangsmåde til fremstilling af syntesegas
US20140103259A1 (en) 2011-04-07 2014-04-17 BioMethanol CHemie Nederland B.V Multi-tubular steam reformer and process for catalytic steam reforming of a hydrocarbonaceous feedstock
EP2707324A1 (en) 2011-05-10 2014-03-19 BioMethanol Chemie Nederland B.V. A process for catalytic steam reforming of a feedstock comprising an oxygenated hydrocarbon and a hydrocarbon
KR101918332B1 (ko) 2011-07-29 2018-11-13 옥세아 코포레이션 개선된 옥소 공정 및 폐유로부터 합성 가스를 생성시키는 방법

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU925414A1 (ru) * 1980-09-15 1982-05-07 Московский ордена Трудового Красного Знамени технологический институт пищевой промышленности Способ распылени жидкости
US4927857A (en) * 1982-09-30 1990-05-22 Engelhard Corporation Method of methanol production
US6048472A (en) * 1997-12-23 2000-04-11 Air Products And Chemicals, Inc. Production of synthesis gas by mixed conducting membranes
SE0004185D0 (sv) * 2000-11-15 2000-11-15 Nykomb Synergetics B V New process
CA2447471A1 (en) * 2001-05-15 2002-11-21 Yasushi Sekine Method and apparatus for liquid-phase reforming of hydrocarbon and oxygen-containing compound
US6699457B2 (en) * 2001-11-29 2004-03-02 Wisconsin Alumni Research Foundation Low-temperature hydrogen production from oxygenated hydrocarbons
US7262334B2 (en) * 2002-11-13 2007-08-28 Regents Of The University Of Minnesota Catalytic partial oxidation of hydrocarbons
DK2064149T3 (da) 2006-09-08 2012-05-07 Gelato Corp N V Fremgangsmåde til fremstilling af syntesegas
CN100462299C (zh) * 2007-05-10 2009-02-18 天津大学 以生产生物柴油的副产物甘油蒸汽重整制合成气的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104702892A (zh) * 2013-12-09 2015-06-10 深圳市盛思维科技有限公司 基于Mesh网络的实时视频传输系统及其方法
CN105947979A (zh) * 2016-04-28 2016-09-21 中国科学院广州能源研究所 一种甲醇-甘油协同水蒸气重整制氢方法及用于该制氢方法的催化剂
CN105947979B (zh) * 2016-04-28 2017-10-27 中国科学院广州能源研究所 一种甲醇‑甘油协同水蒸气重整制氢方法及用于该制氢方法的催化剂

Also Published As

Publication number Publication date
US8372310B2 (en) 2013-02-12
CO6300857A2 (es) 2011-07-21
RU2010141538A (ru) 2012-04-20
RU2494958C2 (ru) 2013-10-10
DK2271583T3 (da) 2019-09-02
WO2009112476A1 (en) 2009-09-17
BRPI0909327A2 (pt) 2015-08-18
ZA201006669B (en) 2011-05-25
CN101990517B (zh) 2014-05-21
EP2271583B1 (en) 2019-06-26
NZ588003A (en) 2012-07-27
EP2103567A1 (en) 2009-09-23
EP2271583A1 (en) 2011-01-12
ES2743411T3 (es) 2020-02-19
US20110006262A1 (en) 2011-01-13
BRPI0909327B1 (pt) 2019-07-09

Similar Documents

Publication Publication Date Title
CN101990517B (zh) 制备合成气的方法ii
CN101362973B (zh) 一种用甲醇制取氢和二甲醚混合燃料的工艺方法
CN205235935U (zh) 用于从含氧化合物生产烯烃的设备
TWI579266B (zh) 使用反應性蒸餾以製備二醇酯的方法
CN100463897C (zh) 一种从乙酸与混合c4反应后的混合物中分离乙酸仲丁酯的方法
JP2012531475A5 (zh)
CN109053355B (zh) 一种连续精馏提纯联苯的方法
Kiss et al. Revamping dimethyl ether separation to a single‐step process
NZ601371A (en) Process for the production of ethanol by hydrogenation of vaporized acetic acid
ATE217893T1 (de) Verfahren zur herstellung von polycarbonaten mit terminalen oh-gruppen
EP2729433B1 (en) Process for producing olefins with heat transfer from steam cracking to alcohol dehydration process.
CN102656121A (zh) 一种净化工艺冷凝液的方法
KR102304228B1 (ko) 디메틸에테르 반응기의 생성물 스트림에 대한 분리가공방법
AU4084001A (en) Process for the preparation of propane-1,3-diol by vapor phase hydrogenation of 3-hydroxypropanal, beta-propiolactone, oligomers of beta-propiolactone, esters of 3-hydroxypropanoic acid or mixtures thereof
TWI417272B (zh) 製程
RU2013127674A (ru) Получение уксусной кислоты с увеличенной скоростью получения
MY158397A (en) Process and apparatus for producing dimethyl ether from methanol
CN108863793A (zh) 一种乙酸异丙酯的制备方法
JP2007269707A (ja) メタクリル酸メチルの製造方法
US10519383B2 (en) Integrated methanol separation and methanol-to-gasoline conversion process
KR101291651B1 (ko) 이소부텐 및 부텐-1의 제조 방법 및 제조 장치
JP6407797B2 (ja) 炭酸ジアルキルの製造方法
AU2015340496B2 (en) Conversion of oxygenates in purge from raw methanol evaporator
TW201213299A (en) Method and apparatus for preparing multiple esters
CN109153921A (zh) 内部发热材料结合烃裂解

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant