CN1051987C - 制备乙炔和合成气的方法 - Google Patents

制备乙炔和合成气的方法 Download PDF

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CN1051987C
CN1051987C CN95108550A CN95108550A CN1051987C CN 1051987 C CN1051987 C CN 1051987C CN 95108550 A CN95108550 A CN 95108550A CN 95108550 A CN95108550 A CN 95108550A CN 1051987 C CN1051987 C CN 1051987C
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acetylene
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P·帕斯勒
R·菲泽
Ｈ·Ｇ·蒂伦
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    • 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
    • C01B3/36—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 oxygen or mixtures containing oxygen as gasifying agents
    • C01B3/363—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 oxygen or mixtures containing oxygen as gasifying agents characterised by the burner used
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/78—Processes with partial combustion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling

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Abstract

用氧通过烃的部分氧化制备乙炔和合成气的方法，原料气首先分别地预热，然后在混合区中充分混合，在流过燃烧器区段后反应，然后，迅速冷却。该燃烧器区段具有若干连续的管道。按照本发明，燃烧器区段的管道是用具有穿孔的板覆盖进口端。

Description

制备乙炔和合成气的方法
本发明涉及用氧通过烃的部分氧化，  制备乙炔和合成气的方法。原料气首先分别地预热，在混合区中充分混合，在其流过燃烧器区段后进行反应，接着，迅速冷却。该燃烧器区段具有若干连续管道。
过去，对于通过烃的部分氧化制备乙炔和合成气的方法，业已作过多次描述(参见inter alia DE 1259875，DE2947005，US3242224)。将甲烷(天然气)部分氧化成乙炔和合成气，尤其在国际上具有工业重要性。而在工业上，单独地由天然气通过部分氧化制备合成气是一种简单方法。与乙炔制备关联的合成气制备方法是与精确的空间、时间、容积条件有关。因此，原料天然气和氧气通常分别地预热，基本上达到摄氏700度，其在混合区中充分混合，并在流过燃烧器区段后进行反应。所用的氧气与天然气的体积比约为0.6。
燃烧器区段包括给定数目的管道，其中为了防止火焰吹回混合室，反应的氧气/天然气混合物的速度应高于火焰速度。继燃烧器区段之后的反应室应具有这样尺寸，即其尺寸使在给定的原料流速下，含乙炔的反应气、裂化气的停留时间仅为几毫秒。过了这段时间后，在这段期间内，相当摄氏1500-2000度高温的平衡不可能被建立。反应产物应立即用水或优选用残余油基本上骤冷至低于摄氏300度，这样能使形成的乙炔不分解成烟灰和氢。通常，这些工艺过程是在大气压或稍高压力下进行。除此天然气外，所有气态或易挥发的烃可以在稍微改变的工艺条件下被使用。然而所有方法的变种都具有缺点，即一次性计算或凭经验确定的反应器尺寸确定了所限定的乙炔和粗制合成气的生产能力，乙炔与合成气之比几乎保持恒定。这导致下面事实，即当乙炔需要减少时，与合成气关联的产物的生产也减少，这样，相关产品的生产，例如甲烷的生产也减少。
本发明目的是改进通过部分氧化烃制备乙炔和合成气的已知方法，用这种改进方法使得在乙炔和合成气的关联生产中，所产生的乙炔和合成气之比可在广泛范围内变化。
我们业已发现，本发明目的可通过用穿孔板覆盖然烧器区段的管道进口端来实现。
本发明方法得使氧与烃之比在广泛的范围内变化而无预燃发生成为可能。而在已知方法中，氧与烃之比仅能在窄范围内变化。本发明方法令人吃惊的是能增加氧与烃之比，以致达到这样程度，即，裂化气中，乙炔的含量极大地减少。很显然，本发明方法，其可通过对现有燃烧器区段的改进来实现，其可被转换成生产高至低含量乙炔的方法，而元任何复杂性，即，通过原料比由低变高，使燃烧器被转换，这使之有很大适应性。这在实践中是非常重要的。
在以下情况下，即在燃烧器区段的空心管道(成组管)中，气体速度为50-150m/s，优选100m/s，在穿孔板中，气体速度为100-300，优选200m/s，相当于2∶1的面积比，则配备给定量管道的燃烧器区段和燃烧器(反应器)具有高范围生产力，因而能适应生产要求。
管道的直径和数目决定燃烧器区段或燃烧器的额定生产力。按照本发明，管道直径为15-45mm是技术上有利的，优选20-35mm。管道的数目为50-150，优选127。板上钻孔的直径为2.5-7mm，优选3-6mm。
参考附图举列的实施例能更好理解本发明的细节和优点。在图中：
图1表示公知的进行部分氧化的设备图；
图2表示图1的燃烧器区段的放大剖面图；
图3表示实施本发明方法的燃烧器区段的极详细放大图；
图4表示本发明盖板的平面图。
图1和图2的公知设备选自“Ullmann′s Encyclopedia ofIndustrial Chemistry. Vol. A1. 1985.107页”。通过管线1，氧加入到设备中，烃是在预热状态下通过管线2加入的。在区域3中，组分如此迅速混合，以致不会形成具有足够高氧浓度，以致能发生预燃的区域。然后，混合物通过扩散器4进入燃烧器区段5，并通过管道6进入反应区7。用由燃烧器区段低端，即反应室开头部分，排出的多重辅助火焰，瞬间地和均匀地点燃反应器中的混合物。
冷却剂是通过管线8经由骤冷管9加入到骤冷容器10的内部。裂化气通过管线11由设备排出，12是骤冷用的冷却剂的出口。
图2没有详细描述燃烧器区段5；仅显示出本发明要点是采用具有钻孔的平行管道6，使扩散器4和反应器7联通。
图3是图2燃烧器区段5剖面的扩大简图。本发明与现有燃烧器区段的主要差别在于管道6的顶端是用板14覆盖，该顶端在反应器7对面。板14截面上规则地分布钻孔13。管道6直径一般为15-45mm，穿孔直径为2.5mm-7mm，优选约4mm。板14的厚度为2mm-8mm，优选约3mm。
板材必须是耐热的。
在现有设备中，不是用穿孔板一个一个单独地覆盖燃烧器单元的管道，而是用板覆盖整个燃烧器区段，在燃烧器区段的管道张开处仅具有相当的钻孔。用特别简单方式，即每个管道末端上具有按本发明要求的钻孔数目，以这样方式，也能使整个板具有钻孔。
在下面实施例中，采用钢性燃烧器区段，其中管道直径为27mm。每单元管子配给19个钻孔，每孔直径为4.2mm，以这样方式、用穿孔板覆盖每个管子。
板子厚度为3mm，板子材料为Incoloy 800。
实施例1-8
在下面表中列举的所有实施例中，原料天然气和氧气分别地加热至摄氏600度，在混合器3中充分混合，并在流过扩散器4和燃烧器区段5后进行反应。在经过几毫秒反应时间后，用芳香性重油将含乙炔的裂化气骤冷至约摄氏250度。然后，用已知方法，通过分馏吸收，分馏成产物乙炔和粗制合成气，接着，用合适的溶剂解吸。
   试验     1    2     3     4     5     6     7     8
 m3(S.T.P)/h氧   4267   4255   4268   4264   3669   3674   3662   3668
m3(S.T.P)/h天然气 6699 6207 5709 5216 5714 5294 4970 4544
 氧与天然气之比   0.637   0.686   0.748   0.817   0.642   0.694   0.737   0.807
 裂化气中乙炔的体积％   7.45   4.56   1.54   1.45   6.91   4.15   1.81   1.43
 Kg/h乙炔   1134   701   239   233   903   557   236   181
 m3(S.T.P)/h合成气   11990   12500   13011   13468   10359   10965   10917   10629
 m3(S.T.P)(合成气)/吨(乙炔)   10573   17832   54439   57802   11472   19686   46258   58724

Claims (6)

1.用氧通过烃的部分氧化制备乙炔和合成气的方法，该方法包括将原料气首先分别地预热，在反应区中充分混合，在流过燃烧器区段后反应，然后迅速冷却，在具有大量连续管道的燃烧器区段，其中燃烧器区段(5)的管道(6)是用具有穿孔(13)的板(14)覆盖进口端。
2.如权利要求1的方法，其中管道(6)直径为15mm-45mm，穿孔(13)的直径为2.5mm-7mm。
3.如权利要求1或2的方法，其中每个单独管道(6)进口端有一个具有穿孔(13)的不相连的板(14)。
4.一种用氧通过烃的氧化作用来制备乙炔和合成气的设备，该设备具有一个混合室(4)，一个具有管道(6)可连通反应器(7)的燃烧器区段(5)，其中燃烧器区段(5)的管道(6)是用穿孔(13)的板覆盖进口端。
5.如权利要求4的设备，其中管道(6)直径为15mm-45mm，穿孔(13)的直径2.5mm-7mm。
6.如权利要求4或5的设备，其中每个单独的管道(6)是用具有穿孔(13)的不相连板(14)覆盖进口端。
CN95108550A 1994-06-29 1995-06-29 制备乙炔和合成气的方法 Expired - Lifetime CN1051987C (zh)

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DE4422815A DE4422815A1 (de) 1994-06-29 1994-06-29 Verfahren zur Herstellung von Acetylen und Synthesegas
DEP4422815.5 1994-06-29

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CN100360479C (zh) * 2000-05-03 2008-01-09 英国石油化学品有限公司 烃的催化氧化方法

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EP0690036B1 (de) 1997-10-22
CN1126193A (zh) 1996-07-10
DE4422815A1 (de) 1996-01-04
NO952602L (no) 1996-01-02
NO305071B1 (no) 1999-03-29
EP0690036A1 (de) 1996-01-03
US5789644A (en) 1998-08-04
NO952602D0 (no) 1995-06-28
DE59500837D1 (de) 1997-11-27
CA2152222A1 (en) 1995-12-30

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