TWI503410B - Methods and apparatus for production of synthesis gas - Google Patents
Methods and apparatus for production of synthesis gas Download PDFInfo
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- TWI503410B TWI503410B TW100107157A TW100107157A TWI503410B TW I503410 B TWI503410 B TW I503410B TW 100107157 A TW100107157 A TW 100107157A TW 100107157 A TW100107157 A TW 100107157A TW I503410 B TWI503410 B TW I503410B
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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
- C01B3/38—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
- C01B3/384—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 the catalyst being continuously externally heated
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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
- 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
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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Description
本發明是關於將天然氣體等的烴系化合物氣體進行改質，以產生由氫與一氧化碳所構成之合成氣體的合成氣體製造方法及裝置。The present invention relates to a method and an apparatus for producing a synthesis gas in which a hydrocarbon-based compound gas such as a natural gas is reformed to produce a synthesis gas composed of hydrogen and carbon monoxide.
以氫與一氧化碳為主成分之合成氣體係在有機合成的原料用途上被廣泛使用，今後，可預測到以各種比例將氫與一氧化碳調和之合成氣體的需求將逐漸增大。其中，例如在費托(Fischer-Tropsch)合成、甲醇合成、二甲醚合成等的有機合成中，期望H2 /CO比為1～2左右之較低者的案例逐漸增加。A synthesis gas system containing hydrogen and carbon monoxide as a main component is widely used for raw materials for organic synthesis, and in the future, it is predicted that the demand for synthesis gas in which hydrogen and carbon monoxide are blended in various ratios will gradually increase. Among them, for example, in organic synthesis such as Fischer-Tropsch synthesis, methanol synthesis, and dimethyl ether synthesis, the case where the lower H 2 /CO ratio is about 1 to 2 is expected to increase.
然而，在製造以氫與一氧化碳為主成分，H2 /CO比為1～2左右的合成氣體、CO氣體等之方法，下述的式子(1)所表示之甲烷的碳酸氣體改質法為有用的。However, in the method of producing a synthesis gas or a CO gas having hydrogen and carbon monoxide as a main component and having a H 2 /CO ratio of about 1 to 2, the carbonic acid gas reforming method of methane represented by the following formula (1) is used. Useful.
CH4 +CO2 →2H2 +2CO… (1)CH 4 +CO 2 →2H 2 +2CO... (1)
其中，除了甲烷與碳酸氣體外，另外將氧作為原料氣體供給至反應器，在相同觸媒上進行燃燒反應與改質反應之熱中和式碳酸氣體改質處理，在設備的縮小、檢修費用的減少的面上極為有利。In addition to methane and carbonic acid gas, oxygen is supplied as a raw material gas to the reactor, and the heat-neutralized carbonic acid gas reforming treatment of the combustion reaction and the reforming reaction is performed on the same catalyst, and the equipment is reduced and repaired. The reduced surface is extremely advantageous.
在下述的專利文獻1，有關於使用四元系觸媒之熱中和式碳酸氣體改質反應的記載。但，本專利文獻僅在其實施例揭示「CH4 的部分氧化反應」及「外部加熱方式的CH4 之碳酸氣體/水蒸氣共改質反應」。即，實際上未揭示有不進行來自於外部之加熱而進行改質之內容。Patent Document 1 listed below discloses a modification process of a heat neutralization type carbonic acid gas using a quaternary catalyst. However, this patent document discloses only "partial oxidation reaction of CH 4 " and "carbonation gas/water vapor co-modification reaction of CH 4 by external heating method" in the examples. That is, it is not actually disclosed that the content is modified without performing heating from the outside.
在下述的專利文獻2，實施不含蒸氣之外部加熱方式的碳酸氣體改質反應。但，在本專利文獻，添加進行反應所需之碳酸氣體量的12倍之碳酸氣體。In the following Patent Document 2, a carbonic acid gas reforming reaction using a vapor-free external heating method is carried out. However, in this patent document, carbon dioxide gas which is 12 times the amount of carbonic acid gas required for the reaction is added.
在下述的專利文獻3，揭示有與熱中和式碳酸氣體改質反應類似之內部熱供給式碳酸氣體改質反應。但，本專利文獻僅在實施例中揭示藉由反應輔助用的加熱器從外部補助進行改質反應所需之熱的一部分之反應器。Patent Document 3 listed below discloses an internal heat supply type carbonic acid gas reforming reaction similar to the heat neutralization type carbonic acid gas reforming reaction. However, this patent document discloses only a reactor in which a part of the heat required for the reforming reaction is externally supplemented by a heater for reaction assistance in the examples.
即，不論哪一個專利文獻皆為著眼於檢驗改質觸媒的活性之基礎研究的專利文獻，並非揭示本質上「不進行外部加熱之改質方法」及「不會過度地添加碳酸氣體之有效地抑制碳析出的改質方法」之實用條件下的熱中和式碳酸氣體改質方法。如此，實際上，不論哪一個專利文獻均未到達實用等級之合成氣體製造裝置。That is, no matter which patent document is a patent document focusing on the basic research for examining the activity of the modified catalyst, it does not disclose the "modification method without external heating" and "effectively not excessively adding carbonic acid gas". A method of modifying a hot neutral type carbonic acid gas under practical conditions of a method for suppressing carbon deposition. Thus, in fact, none of the patent documents has reached the practical level of the synthesis gas production apparatus.
專利文獻1Patent Document 1
日本特開平8-239201號公報Japanese Patent Publication No. 8-239201
專利文獻2Patent Document 2
日本特開平5-270802號公報Japanese Patent Laid-Open No. 5-270802
專利文獻3Patent Document 3
日本特開2004-099363號公報Japanese Special Report 2004-099363
專利文獻4Patent Document 4
日本特開2008-136907號公報Japanese Special Publication No. 2008-136907
非專利文獻1Non-patent document 1
岸田昌浩，新能源‧產業技術總合開發機構-平成14年度-產業技術研究助成事業研究成果報告書，P.2，(2003)Kishada Masahiro, New Energy ‧ Industrial Technology Development Co., Ltd. - Heisei 14 - Industrial Technology Research Assistance Research Report, P.2, (2003)
非專利文獻2Non-patent document 2
程島真哉，配管技術，Vol.51，No.1，P.8～P.12，(2009)Chengdao Shinji, Piping Technology, Vol.51, No.1, P.8~P.12, (2009)
如此，在熱中和式碳酸氣體改質反應，存在有「實用條件下之熱中和式碳酸氣體改質方法的確立」及「在實用條件下之觸媒上的有無碳析出之掌握」這2個問題。In this way, in the heat-reduction type carbonic acid gas reforming reaction, there are two "establishment methods of the heat-neutralized carbonic acid gas reforming under practical conditions" and "the mastery of the carbon-free precipitation on the catalyst under practical conditions". problem.
(1)實用條件下之熱中和式碳酸氣體改質方法的確立(1) Establishment of a heat neutralization type carbonic acid gas upgrading method under practical conditions
在熱中和式碳酸氣體改質反應，對烴的燃燒反應與碳酸氣體改質反應，分別需要具有高活性之觸媒。在專利文獻1，針對上述四元系觸媒具有兩活性乙事，依據個別的實驗加以驗證，但，針對將烴、碳酸氣體及氧同時地導入至反應器之熱中和式碳酸氣體改質反應並未實施。因此，不僅是原料組成、溫度、壓力等能夠有效地使合成氣體產生之改質條件的制訂，就連完全不進行外部加熱之熱中和式碳酸氣體改質反應成立的內容也未進行確認。In the heat neutralization type carbonic acid gas reforming reaction, the combustion reaction of the hydrocarbon and the carbonic acid gas reforming reaction respectively require a catalyst having high activity. Patent Document 1 has two active activities for the above quaternary catalyst, and is verified according to individual experiments, but for the heat neutralization type carbonic acid gas reforming reaction in which hydrocarbons, carbonic acid gas, and oxygen are simultaneously introduced into the reactor. Not implemented. Therefore, not only the raw material composition, temperature, pressure, and the like, which can effectively reform the synthesis gas, but also the content of the heat neutralization type carbonic acid gas reforming reaction without external heating is confirmed.
(2)在實用條件下之觸媒上的有無碳析出之掌握(2) Mastery of carbon precipitation on the catalyst under practical conditions
如前述非專利文獻1、非專利文獻2等所記載，在碳酸氣體改質反應，不僅是熱中和式，只要在反應過程中，於改質觸媒上析出碳，會成為觸媒活性的降低、反應器阻塞等的障礙之原因乙事為眾所皆知。As described in Non-Patent Document 1 and Non-Patent Document 2, the carbonation gas reforming reaction is not only a thermal neutralization type, but also precipitation of carbon on the reforming catalyst during the reaction, which causes a decrease in catalytic activity. The cause of obstacles such as reactor blockage is well known.
因此，不會伴隨碳析出產生之改質觸媒的研究開發，現在也正盛行中，例如前述專利文獻1所記載的改質觸媒之特徵為同時具備高改質反應活性與高碳析出耐性。Therefore, research and development of a modified catalyst which does not occur with carbon deposition is now in progress. For example, the modified catalyst described in Patent Document 1 is characterized by having both high-modification reactivity and high carbon precipitation resistance. .
但，此專利文獻1僅是揭示藉由外部加熱來控制改質器內的溫度之實施例、或過剩地供給作為氧化劑之蒸氣、碳酸氣體等之實施例。即，關於完全不進行外部加熱且以適當的原料氣體組成來實施熱中和式碳酸氣體改質反應，能夠充分地抑制碳的析出之技術完全並未提到。However, this Patent Document 1 merely discloses an embodiment in which the temperature in the reformer is controlled by external heating, or an embodiment in which steam, carbonic acid gas or the like as an oxidizing agent is excessively supplied. In other words, the technique of performing the heat neutralization type carbonic acid gas reforming reaction with no appropriate external heating and having a suitable material gas composition, and sufficiently suppressing the precipitation of carbon is not mentioned at all.
又，作為防止觸媒上之碳析出的手段，添加氧化劑(蒸氣、碳酸氣體等)之方法為眾所皆知。例如在前述專利文獻4，對內部熱供給型碳酸氣體改質方式的原料氣體添加蒸氣。藉此，在改質觸媒上，與碳酸氣體改質反應並行地進行水蒸氣改質反應，變得不易引起因烴的分解反應所產生之碳析出。且，因原料中的蒸氣分壓提高，下述的式子(2)所示的析出碳的氣體化反應行進，其結果，抑制了碳析出。Further, as a means for preventing carbon deposition on the catalyst, a method of adding an oxidizing agent (such as steam or carbonic acid gas) is well known. For example, in the aforementioned Patent Document 4, steam is added to the material gas of the internal heat supply type carbonic acid gas reforming method. As a result, the reforming catalyst is subjected to a steam reforming reaction in parallel with the carbonic acid gas reforming reaction, and it is less likely to cause carbon deposition due to decomposition reaction of hydrocarbons. In addition, the vaporization reaction of the precipitated carbon represented by the following formula (2) proceeds as the vapor partial pressure in the raw material increases, and as a result, carbon deposition is suppressed.
C+H2 O→CO+H2 …(2)C+H 2 O→CO+H 2 ...(2)
另外，為了添加蒸氣，需要進行純水製造裝置、蒸氣產生裝置等的設備之增設及維修，其結果，亦會造成合成氣體製造成本提高。又，就算作為一氧化碳製造處理及裝置，由於一氧化碳的產生量減少，故，蒸氣之添加並不適當。且，因添加蒸氣，會變得容易引起下述的式子(3)所示的甲烷的水蒸氣改質反應、式子(4)所示的一氧化碳的轉化反應，造成特地所製造的CO因反應而被消耗，形成所產生之合成氣體的H2 /CO比變高，並不適合來作為製造H2 /CO比為1～2左右的合成氣體之處理。Further, in order to add steam, it is necessary to add and maintain equipment such as a pure water production device and a steam generation device, and as a result, the production cost of the synthesis gas is also increased. Further, even as a carbon monoxide production process and apparatus, since the amount of carbon monoxide generated is reduced, the addition of steam is not appropriate. In addition, when steam is added, the steam reforming reaction of methane represented by the following formula (3) and the carbon monoxide conversion reaction represented by the formula (4) are easily caused, and the CO factor produced by the special purpose is caused. the reaction is consumed, H form the synthesis gas produced 2 / CO ratio becomes high, as not suitable for producing H 2 / CO ratio of about 1 to 2 for the treatment of synthesis gas.
CH4 +H2 O→3H2 +CO …(3)CH 4 +H 2 O→3H 2 +CO ...(3)
CO+H2 O→H2 +CO2 …(4)CO+H 2 O→H 2 +CO 2 (4)
為了添加蒸氣且抑制H2 /CO比之上升，需要使用例如下述(a)(b)(c)(d)這樣的方法。In order to add steam and suppress an increase in the H 2 /CO ratio, it is necessary to use, for example, the following methods (a), (b), (c), and (d).
(a)增加原料的氧之量。(a) Increasing the amount of oxygen in the raw material.
(b)增加原料的碳酸氣體之量。(b) increasing the amount of carbonic acid gas of the raw material.
(c)同時增加原料的碳酸氣體與氧之量。(c) Simultaneously increase the amount of carbonic acid gas and oxygen in the raw material.
(d)使反應壓力上升。(d) Increasing the reaction pressure.
在使用前述(a)(b)(c)(d)的方法之情況，分別會伴隨引起例如下述(A)(B)(C)(D)這種變化。In the case of using the method of the above (a), (b), (c), and (d), a change such as the following (A) (B) (C) (D) is caused, respectively.
(A)反應溫度之高溫化與原料(主要是氧氣體)使用量的增加。(A) The increase in the temperature of the reaction temperature and the increase in the amount of the raw material (mainly oxygen gas) used.
(B)反應效率的降低與原料(主要是碳酸氣體)使用量的增加。(B) A decrease in the reaction efficiency and an increase in the amount of the raw material (mainly carbonic acid gas) used.
(C)原料(所有的原料氣體)使用量的增加。(C) An increase in the amount of raw materials (all raw material gases) used.
(D)反應效率的降低與原料使用量的增加、以及碳析出反應的促進。(D) Reduction in reaction efficiency, increase in the amount of raw materials used, and promotion of carbon deposition reaction.
當反應溫度高溫化時，則會造成設備成本的提升而當原料使用量增加時，則亦會成為提升原料成本之結果。又，反應效率降低時，不僅對所投入之原料使用量，製品氣體的產生效率降低，且會產生需要除去殘留之不純成分的甲烷。且，當碳析出反應被促進時，會造成觸媒的不活性化、改質器阻塞等。When the reaction temperature is raised, the cost of the equipment is increased, and when the amount of raw materials used is increased, it is also a result of increasing the cost of the raw materials. Further, when the reaction efficiency is lowered, not only the amount of the raw material to be used but also the production efficiency of the product gas is lowered, and methane which needs to remove the remaining impure component is generated. Further, when the carbon deposition reaction is promoted, the catalyst is deactivated, the reformer is clogged, and the like.
如此，在獲得1～2左右的低H2 /CO比的合成氣體之情況，對原料氣體添加蒸氣，會造成伴隨高溫化、高壓化之設計條件的不利，及來自原料使用量、反應效率面等之製造成本變高相連。In the case of obtaining a synthesis gas having a low H 2 /CO ratio of about 1 to 2, the addition of steam to the material gas causes disadvantages in design conditions accompanying high temperature and high pressure, and the amount of raw materials used and the reaction efficiency surface. The manufacturing costs are increased.
因此，在熱中和式碳酸氣體改質反應，為了不需添加蒸氣，而可穩定地產生1～2左右的低H2 /CO比的合成氣體，需要確立活用具有高碳析出耐性之四元系觸媒，能夠進行合成氣體的穩定製造之裝置的運轉條件、運轉方法。Therefore, in the heat neutralization type carbonic acid gas reforming reaction, a synthesis gas having a low H 2 /CO ratio of about 1 to 2 can be stably produced without adding steam, and it is necessary to establish a quaternary system having high carbon precipitation resistance. The catalyst is an operating condition and an operation method of a device capable of stably producing a synthesis gas.
本發明是為了解決前述這樣的問題而開發完成之發明，其目的係在於提供不需要將原料氣體增加至需要量以上，可大幅地減低對觸媒之碳析出，能夠穩定地生產1～2左右的低H2 /CO比的合成氣體之合成氣體製造方法及裝置。The present invention has been developed to solve the above problems, and an object of the present invention is to provide a raw material gas that does not need to be increased to a required amount or more, which can greatly reduce carbon deposition to a catalyst, and can stably produce about 1 to 2 A method and apparatus for producing a synthesis gas having a low H 2 /CO ratio synthesis gas.
為了達到前述目的，本發明的合成氣體製造方法係藉由使作為原料氣體之烴系氣體、氧系氣體以及碳酸氣體與觸媒進行接觸反應，產生烴系氣體的燃燒反應及改質反應，來製造主要由氫與一氧化碳所構成之合成氣體的合成氣體製造方法，其特徵為，當前述改質反應起動時，在讓產生前述燃燒反應及改質反應之改質器內升溫至預定的起動開始溫度後，當導入前述原料氣體之際，為了使改質器內的碳析出減少，而預先將碳酸氣體的導入量增量至超出用來獲得預定的合成氣體之反應所需的量之量，在藉由前述原料氣體的導入使得改質器內上升至預定的起動結束溫度後，讓碳酸氣體的導入量減少至進行獲得預定的合成氣體之反應所需要的量。In order to achieve the above object, the synthesis gas production method of the present invention generates a hydrocarbon-based gas combustion reaction and a reforming reaction by bringing a hydrocarbon-based gas, an oxygen-based gas, and a carbonic acid gas as a source gas into contact with a catalyst. A method for producing a synthesis gas mainly comprising a synthesis gas composed of hydrogen and carbon monoxide, characterized in that when the reforming reaction is started, the temperature rise in the reformer for generating the combustion reaction and the reforming reaction is started to a predetermined start. After the introduction of the raw material gas, in order to reduce the carbon deposition in the reformer, the amount of introduction of the carbonic acid gas is increased in advance to an amount exceeding the amount required for the reaction for obtaining the predetermined synthesis gas. After the introduction of the material gas causes the inside of the reformer to rise to a predetermined start end temperature, the amount of introduction of the carbonic acid gas is reduced to the amount required to perform a reaction for obtaining a predetermined synthesis gas.
又，為了達到前述目的，本發明的合成氣體製造裝置係藉由使作為原料氣體之烴系氣體、氧系氣體以及碳酸氣體與觸媒進行接觸反應，產生烴系氣體的燃燒反應及改質反應，來製造由氫與一氧化碳所構成之合成氣體的合成氣體的製造裝置，其特徵為，當前述改質反應起動時，在讓產生前述燃燒反應及改質反應之改質器內升溫至預定的起動開始溫度後，當導入前述原料氣體之際，為了使改質器內的碳析出減少，而預先將碳酸氣體的導入量增量至超出用來獲得預定的合成氣體之反應所需的量之量，在藉由前述原料氣體的導入使得改質器內上升至預定的起動結束溫度後，控制成讓碳酸氣體的導入量減少至進行獲得預定的合成氣體之反應所需要的量。In order to achieve the above object, the synthesis gas production apparatus of the present invention generates a combustion reaction and a reformation reaction of a hydrocarbon-based gas by bringing a hydrocarbon-based gas, an oxygen-based gas, and a carbonic acid gas as a source gas into contact with a catalyst. A manufacturing apparatus for producing a synthesis gas of a synthesis gas composed of hydrogen and carbon monoxide, wherein when the reforming reaction is started, the temperature of the reformer that generates the combustion reaction and the reforming reaction is raised to a predetermined temperature. After the start temperature is started, when the raw material gas is introduced, in order to reduce the carbon deposition in the reformer, the amount of introduction of the carbonic acid gas is increased in advance to exceed the amount required for the reaction for obtaining the predetermined synthesis gas. After the introduction of the raw material gas causes the inside of the reformer to rise to a predetermined start end temperature, it is controlled to reduce the amount of introduction of the carbonic acid gas to an amount required to perform a reaction for obtaining a predetermined synthesis gas.
在本發明的合成氣體製造方法及裝置，當前述改質反應起動時，在讓產生前述燃燒反應及改質反應之改質器內升溫至預定的起動開始溫度後，當導入前述原料氣體之際，為了使改質器內的碳析出減少，而預先將碳酸氣體的導入量增量至超出用來獲得預定的合成氣體之反應所需的量之量，在藉由前述原料氣體的導入使得改質器內上升至預定的起動結束溫度後，讓碳酸氣體的導入量減少至進行獲得預定的合成氣體之反應所需要的量。In the method and apparatus for producing a synthesis gas according to the present invention, when the reforming reaction is started, the temperature of the reformer that generates the combustion reaction and the reforming reaction is raised to a predetermined starting temperature, and then the raw material gas is introduced. In order to reduce the carbon deposition in the reformer, the amount of introduction of the carbonic acid gas is increased in advance to an amount exceeding the amount required for the reaction for obtaining the predetermined synthesis gas, and is changed by the introduction of the aforementioned raw material gas. After the inside of the massifier rises to a predetermined start end temperature, the amount of introduction of the carbon dioxide gas is reduced to the amount required to carry out the reaction for obtaining a predetermined synthesis gas.
藉此，可將裝置起動時的觸媒上的碳析出抑制成極微量，能夠迴避伴隨碳析出之壓力損失的上升、觸媒活性的降低、改質器的阻塞等之障礙。又，特定會引起碳析出之步驟，藉由僅在該有限之步驟內，增加碳酸氣體之量，可將裝置全體所使用之碳酸氣體量抑制在所需最小限度，可避免多餘之原料氣體的增量。Thereby, it is possible to suppress the precipitation of carbon on the catalyst at the time of starting the device to a very small amount, and it is possible to avoid obstacles such as an increase in pressure loss due to carbon deposition, a decrease in catalyst activity, and a blockage of the reformer. Further, in the step of causing carbon deposition, by increasing the amount of carbonic acid gas only in the limited step, the amount of carbonic acid gas used in the entire apparatus can be suppressed to a minimum required, and excess raw material gas can be avoided. Incremental.
其結果，能夠穩定地進行熱中和式碳酸氣體改質反應，不需要使用反應輔助加熱器等的改質器之外部加熱裝置，僅利用在改質器內所產生之燃燒熱，即可達到高CH4 轉化率。又，不需添加蒸氣、過剩的碳酸氣體，在裝置起動後(反應穩定後)也能抑制碳的析出。且，不需要設置外部加熱爐、純水製造裝置、蒸氣產生裝置等，可抑制設備成本增加。又，由於不需要過剩的蒸氣、碳酸氣體等，亦可抑制原料成本增加。As a result, it is possible to stably carry out the heat neutralization type carbonic acid gas reforming reaction, and it is not necessary to use an external heating device of a reformer such as a reaction auxiliary heater, and it is possible to achieve high use only by the combustion heat generated in the reformer. CH 4 conversion rate. Further, it is not necessary to add steam or excess carbonic acid gas, and it is possible to suppress precipitation of carbon after the apparatus is started (after the reaction is stabilized). Further, it is not necessary to provide an external heating furnace, a pure water producing apparatus, a steam generating apparatus, etc., and it is possible to suppress an increase in equipment cost. Further, since excessive vapor, carbonic acid gas, and the like are not required, an increase in the cost of the raw material can be suppressed.
在本發明，在開始導入前述碳酸氣體後，開始進行烴系氣體的導入之情況，特別是在起動時，能夠迴避因本來要被供給至改質反應之烴的一部分因分解反應所消耗的情況產生，可以防止原料效率的降低。又，能夠有效地防止因產生烴的分解反應所引起之碳的析出。In the present invention, after the introduction of the carbonic acid gas, the introduction of the hydrocarbon-based gas is started, and in particular, at the time of starting, it is possible to avoid the consumption of a part of the hydrocarbon to be supplied to the reforming reaction due to the decomposition reaction. Produced to prevent a decrease in the efficiency of the raw material. Further, precipitation of carbon due to decomposition reaction of hydrocarbons can be effectively prevented.
在本發明，在開始導入烴系氣體後，開始進行氧系氣體的導入之情況，能夠迴避在存在有高溫氧下因導入烴造成急遽地產生反應的情況產生，能夠防止危險性變高。In the present invention, when the introduction of the hydrocarbon-based gas is started, the introduction of the oxygen-based gas is started, and it is possible to avoid the occurrence of a rapid reaction due to introduction of hydrocarbons in the presence of high-temperature oxygen, and it is possible to prevent the risk from becoming high.
以下，說明關於本發明的實施形態。Hereinafter, embodiments of the present invention will be described.
首先，使用四元系觸媒，實施完全不進行外部加熱之天然氣體的熱中和式碳酸氣體改質反應的運轉實驗。First, an operation experiment of a heat neutralization type carbonic acid gas reforming reaction of a natural gas body which is not subjected to external heating is carried out using a quaternary catalyst.
圖1係顯示使用於該運轉實驗之熱中和式碳酸氣體改質裝置的概要圖。Fig. 1 is a schematic view showing a heat neutral type carbonic acid gas reforming apparatus used in the running experiment.
此裝置中，用來導入氧之氧導入路1、用來導入碳酸氣體之碳酸氣體導入路2、用來導入作為天然氣體的烴氣體之烴導入路3在原料氣體導入路4匯聚，然後這些原料氣體被導入至改質器5。In this apparatus, an oxygen introduction path for introducing oxygen, a carbonation gas introduction path 2 for introducing carbonic acid gas, and a hydrocarbon introduction path 3 for introducing a hydrocarbon gas as a natural gas are collected in the raw material gas introduction path 4, and then these The material gas is introduced into the reformer 5.
在前述烴導入路3，設有用來除去天然氣體中的惡臭成分之硫磺成分的脫硫器7，並且，設有將在前述脫硫器7之前段進行脫硫的烴氣體予以加熱之烴加熱器8。又，在前述烴導入路3，匯聚有用來導入脫硫用氫氣體之氫氣體導入路9。且，在前述烴導入路3，匯聚有用來導入沖洗用氮氣之氮氣導入路18。In the hydrocarbon introduction path 3, a desulfurizer 7 for removing a sulfur component of a malodorous component in the natural gas body is provided, and a hydrocarbon gas for heating the hydrocarbon gas which is desulfurized in the preceding stage of the desulfurizer 7 is provided. 8. Further, in the hydrocarbon introduction path 3, a hydrogen gas introduction path 9 for introducing a hydrogen gas for desulfurization is collected. Further, in the hydrocarbon introduction path 3, a nitrogen introduction path 18 for introducing nitrogen for flushing is collected.
另外，在前述碳酸氣體導入路2，設有用來將導入的碳酸氣體進行預熱之碳酸氣體加熱器6。又，在氧導入路1、碳酸氣體導入路2、烴導入路3、氫氣體導入路9，分別設有流量調節器10。Further, the carbonic acid gas introduction path 2 is provided with a carbon dioxide gas heater 6 for preheating the introduced carbonic acid gas. Moreover, the flow rate adjuster 10 is provided in each of the oxygen introduction path 1, the carbon dioxide gas introduction path 2, the hydrocarbon introduction path 3, and the hydrogen gas introduction path 9.
又，在前述原料氣體導入路4，設有將匯聚後的氧氣體、碳酸氣體、天然氣體進行預熱的預熱加熱器17。Further, the raw material gas introduction path 4 is provided with a preheating heater 17 for preheating the concentrated oxygen gas, carbonic acid gas, and natural gas.
在前述改質器5，填充四元系的改質觸媒。In the reformer 5 described above, a quaternary modified catalyst is filled.
作為前述四元系的改質觸媒，使用Rh修飾(Ni-CeO2 )-Pt觸媒。又，藉由使用前述Rh修飾(Ni-CeO2 )-Pt觸媒，能夠將烴系氣體的燃燒反應與改質反應在相同反應區域內同時地進行。As the modified catalyst of the above quaternary system, Rh-modified (Ni-CeO 2 )-Pt catalyst was used. Further, by using the Rh-modified (Ni-CeO 2 )-Pt catalyst, the combustion reaction and the reforming reaction of the hydrocarbon-based gas can be simultaneously performed in the same reaction region.
即，在前記觸媒上進行：讓烴的一部分完全燃燒，使烴變換成CO2 與H2 O之燃燒反應、和將藉由此燃燒反應所產生的CO2 與H2 O、及作為原料氣體被導入之CO2 來與殘餘之烴反應，來變換成H2 與CO之改質反應，藉此將烴變換成H2 與CO。That is, the first catalyst in mind: complete combustion so that hydrocarbon portion of the hydrocarbon conversion reaction to CO 2 and H 2 O of the combustion, and the CO 2 and H produced by this combustion reaction of 2 O, as the starting material, and The gas is introduced into the CO 2 to react with the residual hydrocarbons to convert it into a reforming reaction of H 2 and CO, thereby converting the hydrocarbons into H 2 and CO.
前述Rh修飾(Ni-CeO2 )-Pt觸媒係例如藉由在具有適當的表面積之氧化鋁受載體表面受載Rh，接著受載Pt，進一步同時受載Ni與CeO2 來獲得的。但，受載體的材質、形狀等的選擇、有無形成被覆物或其材質之選擇，可做各種變化。The aforementioned Rh-modified (Ni-CeO 2 )-Pt catalyst is obtained, for example, by carrying Rh on the surface of the support having an appropriate surface area, followed by loading of Pt, and further carrying Ni and CeO 2 simultaneously. However, various changes can be made depending on the choice of the material and shape of the carrier, the presence or absence of the formation of the coating or the material thereof.
Rh的受載係藉由含浸Rh的水溶性鹽的水溶液後，再進行乾燥、燒成、氫還原來實施的。又，Pt的受載係藉由含浸Pt的水溶性鹽的水溶液後，進行乾燥、燒成、氫還原來進行。Ni及CeO2 的同時受載係藉由含浸Ni的水溶性鹽及Ce的水溶性鹽的混合水溶液後，進行乾燥、燒成、氫還原來進行的。The loading of Rh is carried out by impregnating an aqueous solution of a water-soluble salt of Rh, followed by drying, firing, and hydrogen reduction. Further, the loading of Pt is carried out by impregnating an aqueous solution of a water-soluble salt of Pt, followed by drying, firing, and hydrogen reduction. The simultaneous loading of Ni and CeO 2 is carried out by drying, calcining, and hydrogen-reducing a mixed aqueous solution of a water-soluble salt of Ni and a water-soluble salt of Ce.
藉由上述所述的方式，獲得所需之Rh修飾(Ni-CeO2 )-Pt觸媒。各成分的組成，在重量比設定成Rh：Ni：CeO2 ：Pt=(0.05-0.5)：(3.0-10.0)：(2.0-8.0)：(0.3-5.0)，期望為設定成Rh：Ni：CeO2 ：Pt=(0.1-0.4)：(4.0-9.0)：(2.0-5.0)：(0.3-3.0)為佳。The desired Rh-modified (Ni-CeO 2 )-Pt catalyst was obtained by the means described above. The composition of each component is set to Rh:Ni:CeO 2 :Pt=(0.05-0.5):(3.0-10.0):(2.0-8.0):(0.3-5.0), and it is desirable to set it to Rh:Ni. : CeO 2 : Pt = (0.1 - 0.4): (4.0 - 9.0): (2.0 - 5.0): (0.3 - 3.0) is preferred.
再者，亦可省略在前述各階段之氫還原處理，當實際使用時，將觸媒以高溫進行氫還原後加以使用。當在各階段已經進行了氫還原處理時，亦可在進一步使用時，將觸媒以高溫進行氫還原後加以使用。Further, the hydrogen reduction treatment at each of the above stages may be omitted, and when actually used, the catalyst may be used after hydrogen reduction at a high temperature. When the hydrogen reduction treatment has been carried out at each stage, the catalyst may be used at a high temperature for hydrogen reduction after further use.
藉由填充有前述四元系的改質觸媒之改質器5予以改質而產生之改質氣體(合成氣體)係藉由合成氣體取出路11加以取出，再以冷卻器12冷卻，然後以氣液分離器13除去水分等的液體。在圖中，符號14為冷卻水導入路14、符號15為排水管15。以氣液分離器13除去水分等的液體後之合成氣體，因應需要，藉由未圖示的PSA裝置等加以精製後，輸送至同樣未圖示的合成氣體利用設備後供其利用。The reformed gas (synthesis gas) generated by reforming the reformer 5 filled with the modified catalyst of the quaternary system is taken out by the synthesis gas take-out path 11 and then cooled by the cooler 12, and then The liquid such as moisture is removed by the gas-liquid separator 13. In the figure, reference numeral 14 denotes a cooling water introduction path 14, and reference numeral 15 denotes a drain pipe 15. The synthesis gas obtained by removing the liquid such as water by the gas-liquid separator 13 is purified by a PSA apparatus (not shown) or the like, and then sent to a synthesis gas utilization apparatus (not shown) for use.
在此運轉實驗所使用的天然氣體的組成係如下述。The composition of the natural gas used in the operation experiment here is as follows.
CH4 =89～90%CH 4 =89~90%
C2 H6 =5～6%C 2 H 6 = 5 to 6%
C3 H8 =2～3%C 3 H 8 = 2 to 3%
C4 H10 =1～2%C 4 H 10 =1~2%
又，在熱中和式碳酸氣體改質反應，主要是前述的式子(1)(3)(4)及下述的式子(5)的反應連續地引起所致。Further, in the heat neutralization type carbonic acid gas reforming reaction, mainly the reaction of the above formula (1) (3) (4) and the following formula (5) is continuously caused.
CH4 +2O2 →CO2 +2H2 O… (5)CH 4 +2O 2 →CO 2 +2H 2 O... (5)
且，關於氣體內的微量成分之C2 H6 、C3 H8 、C4 H10 ，均經過上述的式子(1)(3)(5)以及下述的式子(6)所示的反應過程者。Further, C 2 H 6 , C 3 H 8 and C 4 H 10 of a trace component in the gas are subjected to the above formulas (1), (3) and (5) and the following formula (6). The process of the reaction.
Cn H2n+2 +(3n+1)/2O2 →nCO2 +(n+1)H2 O… (6)C n H 2n+2 +(3n+1)/2O 2 →nCO 2 +(n+1)H 2 O... (6)
(但，n=2～4)(However, n=2~4)
此運轉實驗之條件係依據來自於上述的天然氣體組成與式子(1)及(3)～(6)之平衡計算的模擬結果，設定原料氣體組成、改質溫度、改質壓力，使得合成氣體中的H2 /CO比在理論上大致成為1。The conditions of this operation experiment are based on the simulation results from the above-mentioned calculation of the balance between the composition of the natural gas and the equations (1) and (3) to (6), setting the composition of the raw material gas, the temperature of the reforming, and the pressure of the reforming, so that the synthesis The H 2 /CO ratio in the gas is theoretically approximately 1.
具體而言，CO2 /C=0.9～1.1、O2 /C=0.55～0.60、改質觸媒入口的原料氣體溫度為350～400℃、改質器之出口壓力為50～100kPaG。Specifically, CO 2 / C = 0.9 to 1.1, O 2 / C = 0.55 to 0.60, the raw material gas temperature of the modified catalyst inlet is 350 to 400 ° C, and the outlet pressure of the reformer is 50 to 100 kPaG.
在此，CO2 /C、O2 /C係指下述內容。Here, CO 2 /C, O 2 /C means the following.
CO2 /C=(原料氣體中的CO2 [mol])/(天然氣體中的C[mol])CO 2 /C=(CO 2 [mol] in the raw material gas) / (C [mol] in the natural gas)
O2 /C=(原料氣體中的O2 [mol])/(天然氣體中的C[mol])O 2 /C=(O 2 [mol] in the raw material gas) / (C [mol] in the natural gas)
當在此條件下進行運轉實驗時，在裝置起動時(剛反應開始後)，於觸媒上有多量的碳析出。這是由於即使在使用具有高碳析出耐性之四元系觸媒的情況，在將氫與一氧化碳以等mol量產生之條件下之碳酸氣體改質反應中，不易避免裝置起動時的碳析出之故。When the operation experiment was carried out under these conditions, a large amount of carbon was precipitated on the catalyst at the start of the apparatus (just after the start of the reaction). This is because even in the case of using a quaternary catalyst having high carbon precipitation resistance, in the carbonic acid gas reforming reaction under the condition that hydrogen and carbon monoxide are generated in an equal molar amount, it is difficult to avoid carbon deposition at the time of starting the apparatus. Therefore.
如此，即使單純的模擬測試條件下運轉，也因為裝置起動時之碳析出，成為壓力損失的異常增大、改質器等的阻塞之原因，無法使裝置的起動程序正常地起動，依然並未解決前述的「實用條件下之熱中和式碳酸氣體改質方法的確立」及「在實用條件下之觸媒上的有無碳析出之掌握」之問題。In this way, even if the operation is performed under simple simulation test conditions, the carbon deposition during the startup of the device causes an abnormal increase in pressure loss and a blockage of the reformer, etc., and the startup procedure of the device cannot be normally started. Solve the above-mentioned problem of "establishment of a method for upgrading a hot-neutralized carbonic acid gas under practical conditions" and "presence of carbon deposition on a catalyst under practical conditions".
圖2係顯示此裝置之起動程序的流程圖。Figure 2 is a flow chart showing the starting procedure of the device.
即，裝置的起動開始後，進行以下的步驟1～步驟4。That is, after starting the start of the apparatus, the following steps 1 to 4 are performed.
(步驟1)在升溫步驟，將改質觸媒入口的原料氣體溫度升溫至350～400℃。(Step 1) In the temperature increasing step, the temperature of the material gas at the reforming catalyst inlet is raised to 350 to 400 °C.
(步驟2)在碳酸氣體導入開始步驟，以成為CO2 /C=0.9～1.1之流量，開始進行碳酸氣體的導入。(Step 2) In the carbon dioxide gas introduction start step, introduction of carbonic acid gas is started at a flow rate of CO 2 / C = 0.9 to 1.1.
(步驟3)在烴導入步驟，開始進行作為天然氣體之烴氣體的導入。(Step 3) In the hydrocarbon introduction step, introduction of a hydrocarbon gas as a natural gas is started.
(步驟4)在氧導入步驟，以成為O2 /C=0.55～0.60之流量，開始進行氧氣體的導入，結束起動。(Step 4) In the oxygen introduction step, introduction of oxygen gas is started at a flow rate of O 2 / C = 0.55 to 0.60, and the startup is completed.
在此起動程序，在步驟4開始進行了大約10分，在觸媒上析出多量的碳，伴隨該析出，造成改質器5內被阻塞。因此，觸媒層之壓力損失，原本在10～15kPa左右，異常上升至250kPa以上，在系統的穩定操作上不理想。Here, the starting procedure was started in step 4 for about 10 minutes, and a large amount of carbon was deposited on the catalyst, and the precipitation was caused to cause the inside of the reformer 5 to be blocked. Therefore, the pressure loss of the catalyst layer is originally about 10 to 15 kPa, and the abnormality rises to 250 kPa or more, which is not preferable in the stable operation of the system.
在此起動程序，裝置起動時，碳析出之原因可考量如下。In this starting procedure, when the device is started, the cause of carbon deposition can be considered as follows.
當裝置起動時，依碳酸氣體、烴、氧的順序，將原料氣體導入至改質器5。然後，在合成氣體中的H2 /CO比大致成為1之條件下，開始導入氧時，則在觸媒上會進行燃燒反應，大約400℃之觸媒層的溫度逐漸上升，最終到達800℃左右。又，碳析出反應係在反應氣體溫度為700℃以下的情況容易產生。因此，當裝置起動時的觸媒層的溫度上升的過程到達碳容易析出之溫度領域時，碳會大量地析出。When the apparatus is started, the raw material gas is introduced into the reformer 5 in the order of carbonic acid gas, hydrocarbons, and oxygen. Then, when the H 2 /CO ratio in the synthesis gas is approximately 1, when the introduction of oxygen is started, the combustion reaction proceeds on the catalyst, and the temperature of the catalyst layer at about 400 ° C gradually rises, eventually reaching 800 ° C. about. Further, the carbon deposition reaction is likely to occur when the reaction gas temperature is 700 ° C or lower. Therefore, when the process of raising the temperature of the catalyst layer at the time of starting the device reaches a temperature range in which carbon is easily precipitated, carbon is precipitated in a large amount.
在此，上述的碳析出反應係可考量為因下述的式子(7)(8)的反應所引起的。Here, the above-described carbon deposition reaction system can be considered to be caused by the reaction of the following formula (7) (8).
2CO→C+CO2 … (7)2CO→C+CO 2 ... (7)
CO+H2 →C+H2 O… (8)CO+H 2 →C+H 2 O... (8)
在此，前述式子(7)(8)為平衡反應，是否有碳析出，係會依據反應氣體中的CO、CO2 、H2 、H2 O的各分壓(pCO)、(pCO2 )、(pH2 )、(pH2 O)與反應氣體溫度來決定。Here, the above formulas (7) and (8) are equilibrium reactions, and whether or not carbon is precipitated, depending on the partial pressure (pCO) of CO, CO 2 , H 2 , and H 2 O in the reaction gas, (pCO 2 ) ), (pH 2 ), (pH 2 O) and reaction gas temperature are determined.
因此，當下述的式子(9)(10)所示的碳活性值A1 、A2 超過1時，則式子(7)(8)會朝右行進而產生碳析出，當碳活性值A1 、A2 低於1時，則，式子(7)(8)會朝左行進而碳氣體化，不會產生析出。Therefore, when the carbon activity values A 1 and A 2 shown in the following formulas (9) and (10) exceed 1, the formula (7) (8) will travel to the right to cause carbon deposition, when the carbon activity value When A 1 and A 2 are less than 1, the formula (7) (8) will travel to the left and carbon will be gasified, and precipitation will not occur.
A1 =K1 ×(pCO)2 /(pCO2 )…(9)A 1 =K 1 ×(pCO) 2 /(pCO 2 )...(9)
A2 =K2 ×(pCO)×(pH2 )/(pH2 O)…(10)A 2 = K 2 × (pCO) × (pH 2 ) / (pH 2 O) (10)
A1 ：對前述式子(7)之碳活性值A 1 : carbon activity value of the above formula (7)
A2 ：對前述式子(8)之碳活性值A 2 : carbon activity value of the above formula (8)
K1 、K2 ：自溫度求取之平衡定數K 1 , K 2 : balance constant from temperature
在熱中和式碳酸氣體改質反應，當依據前述式子(9)(10)算出觸媒層之反應氣體的碳活性值時，則如下述的表1所示得知，當反應氣體大約為700℃以下時，A1 、A2 皆成為1以上，會產生碳析出。In the heat neutralization type carbonic acid gas reforming reaction, when the carbon activity value of the reaction gas of the catalyst layer is calculated according to the above formula (9) (10), as shown in Table 1 below, when the reaction gas is approximately When the temperature is 700 ° C or lower, both A 1 and A 2 are 1 or more, and carbon deposition occurs.
因此，熱中和式碳酸氣體改質反應開始進行後，在反應氣體自400℃逐漸上升而到達700℃期間，在觸媒層上碳會多量析出。Therefore, after the heat neutralization type carbonic acid gas reforming reaction is started, a large amount of carbon is precipitated on the catalyst layer while the reaction gas gradually rises from 400 ° C to reach 700 ° C.
另外，在起動初期，當自最初即作成為700℃以上的高溫時，則不僅在之後的熱中和反應之反應溫度為上升至1000℃以上造成不易控制，並且亦會產生著火、***等的危險性。In addition, in the initial stage of the start-up, when the temperature is high at 700 ° C or higher from the beginning, the reaction temperature of the reaction in the subsequent heat and the reaction is increased to 1000 ° C or more, which is difficult to control, and there is a risk of fire, explosion, and the like. Sex.
因此，在本發明，為了抑制剛開始反應後的觸媒上的碳析出產生，僅在起動初期，將導入至改質器5之作為原料氣體的碳酸氣體的流量增加至大約1.5～2倍。Therefore, in the present invention, in order to suppress generation of carbon deposition on the catalyst immediately after the start of the reaction, the flow rate of the carbonic acid gas as the source gas introduced into the reformer 5 is increased to about 1.5 to 2 times only at the initial stage of starting.
圖3係顯示本發明之裝置的起動程序之流程。Figure 3 is a flow chart showing the starting procedure of the apparatus of the present invention.
在本發明，當前述改質反應起動時，在讓產生前述燃燒反應及改質反應之改質器內升溫至預定的起動開始溫度後，當導入前述原料氣體之際，為了使改質器內的碳析出減少，而預先將碳酸氣體的導入量增量至超出用來獲得預定的合成氣體之反應所需的量之量，在藉由前述原料氣體的導入使得改質器內上升至預定的起動結束溫度後，讓碳酸氣體的導入量減少至進行獲得預定的合成氣體之反應所需要的量。In the present invention, when the reforming reaction is started, after the temperature of the reformer that generates the combustion reaction and the reforming reaction is raised to a predetermined starting temperature, when the raw material gas is introduced, in order to make the reformer The carbon deposition is reduced, and the amount of introduction of the carbonic acid gas is increased in advance to an amount exceeding the amount required for the reaction for obtaining the predetermined synthesis gas, and the inside of the reformer is raised to a predetermined state by introduction of the aforementioned raw material gas. After the end temperature is started, the amount of introduction of the carbonic acid gas is reduced to the amount required to carry out the reaction for obtaining the predetermined synthesis gas.
即，裝置的起動開始後，進行以下的步驟1～步驟5。That is, after the start of the start of the apparatus, the following steps 1 to 5 are performed.
(步驟1)在升溫步驟，自氮氣導入路18將氮氣導入到烴導入路3後，一邊以氮氣沖洗改質器5內，一邊以烴加熱器8及預熱加熱器17加熱氮氣，然後導入至改質器5，將改質觸媒入口的氣體溫度升溫至350～400℃。(Step 1) In the temperature rising step, after the nitrogen gas is introduced into the hydrocarbon introduction path 3 from the nitrogen introduction path 18, the inside of the reformer 5 is flushed with nitrogen, and the nitrogen gas is heated by the hydrocarbon heater 8 and the preheating heater 17, and then introduced. Up to the reformer 5, the temperature of the gas at the inlet of the modified catalyst is raised to 350 to 400 °C.
(步驟2)在碳酸氣體導入開始步驟，以成為定格量的1.5～2倍之CO2 /C=1.5～2.0的流量，開始進行碳酸氣體的導入。此時，碳酸氣體係以碳酸氣體加熱器6及預熱加熱器17予以升溫。(Step 2) In the carbon dioxide gas introduction start step, introduction of carbonic acid gas is started at a flow rate of 1.5 to 2 times the amount of the constant amount of CO 2 / C = 1.5 to 2.0. At this time, the carbon dioxide gas system is heated by the carbon dioxide gas heater 6 and the preheating heater 17.
(步驟3)在烴導入步驟，停止來自於氮氣導入路18之氮氣導入，從烴導入路3開始進行作為天然氣體之烴氣體的導入。(Step 3) In the hydrocarbon introduction step, the introduction of nitrogen gas from the nitrogen introduction path 18 is stopped, and introduction of the hydrocarbon gas as a natural gas is started from the hydrocarbon introduction path 3.
(步驟4)氧導入步驟，在將改質觸媒入口的氣體溫度升溫至350～400℃後，以成為O2 /C=0.55～0.60之流量開始進行氧氣體的導入。藉此，熱中和式碳酸氣體改質反應開始進行。(Step 4) In the oxygen introduction step, after the temperature of the gas at the inlet of the reforming catalyst is raised to 350 to 400 ° C, introduction of oxygen gas is started at a flow rate of O 2 / C = 0.55 to 0.60. Thereby, the heat neutralization type carbonic acid gas reforming reaction starts.
(步驟5)在碳酸氣體減量步驟，在確認到改質觸媒入口的原料氣體溫度成為700℃以上後，開始進行碳酸氣體的減量，將碳酸氣體的流量減少至定格量之CO2 /C=0.9～1.1的流量，結束起動。(Step 5) In the carbon dioxide gas reduction step, after confirming that the temperature of the raw material gas at the inlet of the reforming catalyst becomes 700 ° C or higher, the reduction of the carbon dioxide gas is started, and the flow rate of the carbon dioxide gas is reduced to a constant amount of CO 2 /C = The flow rate of 0.9 to 1.1 ends.
在前述的起動程序，不會產生因碳的析出所引起之急遽的壓力上升，可保持在原本的正常範圍之10kPa左右的壓力損失，能夠使裝置穩定地運轉。In the above-described starting procedure, there is no sudden increase in pressure due to precipitation of carbon, and a pressure loss of about 10 kPa in the normal range can be maintained, and the apparatus can be stably operated.
再者，(步驟1)升溫步驟中，由於當在起動初期即作成高溫，則之後的熱中和反應之反應溫度會上升至1000℃以上，變得不易控制，且亦會產生著火、***等的危險性，故，將改質觸媒入口的氣體溫度作成為400℃以下為佳。Further, in the (step 1) heating step, since the temperature is high in the initial stage of the start, the reaction temperature of the subsequent heat neutralization reaction rises to 1000 ° C or higher, which is difficult to control, and may cause fire, explosion, or the like. The risk is such that the temperature of the gas at the inlet of the modified catalyst is preferably 400 ° C or less.
又，(步驟2)在碳酸氣體導入開始步驟，將CO2 /C作成1.5以上為佳，而將CO2 /C作成1.5以上、2.0以下為更佳。在CO2 /C未滿1.5之情況，無法充分地防止碳析出，相反地當超過2.0時，則會造成原料氣體的使用量不必要地增大，因此並不理想。Further, (Step 2) In the step of introducing the carbonic acid gas, it is preferable to make CO 2 /C 1.5 or more, and it is more preferable to make CO 2 /C 1.5 or more and 2.0 or less. When the CO 2 /C is less than 1.5, carbon deposition cannot be sufficiently prevented. Conversely, when it exceeds 2.0, the amount of use of the material gas is unnecessarily increased, which is not preferable.
又，在(步驟4)，藉由花一些時間來導入氧氣體，能夠使熱中和式反應逐漸穩定，又，使氧氣體的導入流量逐漸增加，而作成為O2 /C=0.55～0.60之流量為佳。Further, in (Step 4), by taking some time to introduce the oxygen gas, the heat neutralization reaction can be gradually stabilized, and the introduction flow rate of the oxygen gas is gradually increased to become O 2 / C = 0.55 to 0.60. The flow rate is better.
又，例如，當預先在開始導入碳酸氣體前，先開始進行烴的導入時，則原本應供給至改質反應之烴的一部分會被分解反應所消耗，原料效率大幅降低，因此，預先在開始進行碳酸氣體導入後即開始烴的導入為佳。In addition, when the introduction of hydrocarbons is started before the introduction of the carbonic acid gas, the part of the hydrocarbon to be supplied to the reforming reaction is consumed by the decomposition reaction, and the efficiency of the raw material is greatly lowered. It is preferred to start the introduction of hydrocarbons after the introduction of the carbon dioxide gas.
又，例如，當在導入烴前，先開始進行氧的導入時，則會因在高溫氧的存在下導入烴，使得急遽地產生反應之危險性變高，因此，在開始進行烴導入後，再開始進行氧的導入為佳。In addition, when introduction of oxygen is started before introduction of hydrocarbons, hydrocarbons are introduced in the presence of high-temperature oxygen, and the risk of rapid reaction is increased. Therefore, after hydrocarbon introduction is started, It is better to start the introduction of oxygen again.
接著，針對使用四元系觸媒時之觸媒上的碳的析出狀態進行驗證。Next, verification is performed on the precipitation state of carbon on the catalyst when the quaternary catalyst is used.
圖4係採用適用本發明之起動程序且以上述的條件進行改質反應後之使用過的觸媒的外觀照片。又，下述的表2係顯示該使用過的觸媒的碳析出量、壓力損失的測定結果。又，作為比較，藉由以上述的以往的起動程序作為比較例，而未使用的觸媒作為初期樣品加以顯示。Fig. 4 is a photograph showing the appearance of a used catalyst which has been subjected to a modification reaction under the above-described conditions by applying the starting procedure of the present invention. Further, Table 2 below shows the measurement results of the amount of carbon deposition and the pressure loss of the used catalyst. Further, for comparison, the conventional starting program described above was used as a comparative example, and the unused catalyst was displayed as an initial sample.
從圖4及表2可得知，在比較例，10重量%以上者，會有多量的碳析出，但，在實施例，僅有0.062重量%之極微量的碳析出。其結果，在比較例，會有250kPa以上之壓力損失，而在實施例則被抑制在10kPa左右，不會產生造成觸媒活性的降低、反應器阻塞等之障礙。As can be seen from Fig. 4 and Table 2, in the comparative example, a large amount of carbon was precipitated in 10% by weight or more, but in the examples, only 0.062% by weight of a very small amount of carbon was precipitated. As a result, in the comparative example, there is a pressure loss of 250 kPa or more, and in the embodiment, it is suppressed to about 10 kPa, and there is no trouble such as a decrease in catalyst activity or a blockage of the reactor.
藉由採用這樣的起動程序，能夠穩定地使裝置起動，可以達到「實用條件下之熱中和式碳酸氣體改質方法的確立」及「在實用條件下之觸媒上的有無碳析出之掌握」。By adopting such a start-up procedure, it is possible to stably start the apparatus, and it is possible to achieve "the establishment of a heat neutral type carbonic acid gas reforming method under practical conditions" and "the presence or absence of carbon deposition on a catalyst under practical conditions". .
在本實施形態所執行之下述的反應條件中，顯示改質反應的效率之CH4 轉化率(在反應時所消耗之CH4 [mol]/原料氣體中的CH4 [mol])係成為99%以上的高數值，不需使用反應輔助加熱器等的改質器5之外部加熱裝置，能夠僅藉由在觸媒層所產生之燃燒反應熱來使改質反應進行。又，合成氣體中的H2 /CO比係為0.98之接近1的值。In the following reaction conditions of the present embodiment is executed, the display efficiency of the reforming reaction CH 4 conversion (CH CH [mol] / material gas consumed during the reaction 4 of 4 [mol]) be based A high value of 99% or more does not require the use of an external heating device of the reformer 5 such as a reaction auxiliary heater, and the reforming reaction can be performed only by the heat of combustion reaction generated in the catalyst layer. Further, the H 2 /CO ratio in the synthesis gas was a value close to 1 of 0.98.
如此，在本實施形態得知，改質反應到達平衡狀態，使用四元系觸媒之熱中和式碳酸氣體改質方法，作為合成氣體製造方法極為有效。As described above, in the present embodiment, it is known that the reforming reaction reaches the equilibrium state and the thermal neutralization type carbonic acid gas reforming method using the quaternary catalyst is extremely effective as a method for producing a synthesis gas.
又，從表2的結果可得知，不僅裝置起動時，在之後的穩定運轉時，碳的析出量呈微量，藉由本發明，可確立裝置起動時、及裝置穩定運轉時不會伴隨有碳的析出之熱中和式碳酸氣體改質方式的合成氣體製造方法。Further, as is clear from the results of Table 2, not only the amount of carbon deposition during the subsequent stable operation but also the amount of carbon deposition is small, and the present invention can establish that carbon is not accompanied when the apparatus is started and the apparatus is stably operated. A method for producing a synthesis gas in which a carbonation gas is reformed by a neutralization type carbonation gas.
若依據本實施形態的起動程序，可獲得以下的效果。According to the starting procedure of the embodiment, the following effects can be obtained.
可將裝置起動時的觸媒上的碳析出抑制成極微量，能夠迴避伴隨碳析出之壓力損失的上升、觸媒活性的降低、改質器5之阻塞等的障礙。It is possible to suppress the precipitation of carbon on the catalyst at the time of starting the device to a very small amount, and it is possible to avoid obstacles such as an increase in pressure loss accompanying carbon deposition, a decrease in catalyst activity, and a blockage of the reformer 5.
在特定會引起碳析出之步驟，藉由僅在該有限之步驟內，增加碳酸氣體之量，可將裝置全體所使用之碳酸氣體量抑制在所需最小限度，可避免多餘之原料氣體的增量。In the step of specifically causing carbon deposition, by increasing the amount of carbonic acid gas only in the limited step, the amount of carbonic acid gas used in the entire apparatus can be suppressed to the minimum required, and the increase of excess raw material gas can be avoided. the amount.
其結果，能夠穩定地進行使用四元系觸媒之熱中和式碳酸氣體改質反應，獲得以下的效果。As a result, the heat neutralization type carbonic acid gas reforming reaction using the quaternary catalyst can be stably performed, and the following effects can be obtained.
不需使用反應輔助加熱器等的改質器5之外部加熱裝置，可僅利用改質器5內所產生之燃燒熱，達到高度的CH4 轉化率。It is possible to achieve a high CH 4 conversion rate by using only the heat of combustion generated in the reformer 5 without using an external heating device of the reformer 5 such as a reaction auxiliary heater.
不需添加蒸氣、過剩的碳酸氣體等，在裝置起動後(反應穩定後)也能抑制碳的析出。It is not necessary to add steam or excess carbonic acid gas, and it is possible to suppress precipitation of carbon after the apparatus is started (after the reaction is stabilized).
不需要另外設置外部加熱爐、純水製造裝置、蒸氣產生裝置等，能夠抑制設備成本。又，由於不需要過剩的蒸氣、碳酸氣體等，故亦可抑制原料成本。It is not necessary to separately provide an external heating furnace, a pure water producing apparatus, a steam generating apparatus, etc., and it is possible to suppress equipment cost. Moreover, since excess steam, carbonic acid gas, etc. are not required, the raw material cost can also be suppressed.
再者，在前述各實施形態，將各原料氣體予以導入的步驟之順序不限於上述者，若當將各原料氣體予以導入之際可增加碳酸氣體的導入量，則亦可變更其他原料氣體的導入順序。In addition, in the above-mentioned respective embodiments, the order of the steps of introducing the respective source gases is not limited to the above, and when the introduction amount of the carbon dioxide gas can be increased when the respective source gases are introduced, the other material gases can be changed. Import order.
1．．．氧導入路1. . . Oxygen introduction
2．．．碳酸氣體導入路2. . . Carbonic acid gas introduction
3．．．烴導入路3. . . Hydrocarbon introduction route
4．．．原料氣體導入路4. . . Raw material gas introduction
5．．．改質器5. . . Modifier
6．．．碳酸氣體加熱器6. . . Carbonic acid gas heater
7．．．脫硫器7. . . Desulfurizer
8．．．烴加熱器8. . . Hydrocarbon heater
9．．．氫氣體導入路9. . . Hydrogen gas introduction path
10．．．流量調節器10. . . Flow regulator
11．．．合成氣體取出路11. . . Syngas extraction path
12．．．冷卻器12. . . Cooler
13．．．氣液分離器13. . . Gas-liquid separator
14．．．冷卻水導入路14. . . Cooling water introduction
15．．．排水管15. . . Drain pipe
17．．．預熱加熱器17. . . Preheating heater
18．．．氮氣導入路18. . . Nitrogen introduction
圖1係顯示使用於本發明之合成氣體製造裝置的圖。Fig. 1 is a view showing a synthesis gas producing apparatus used in the present invention.
圖2係顯示以往的起動程序之步驟圖。Fig. 2 is a view showing the steps of a conventional starting procedure.
圖3係顯示適用本發明之起動程序的步驟圖。Figure 3 is a flow chart showing the starting procedure to which the present invention is applied.
圖4係顯示實施例與比較例的觸媒的狀態之外觀照片。Fig. 4 is a photograph showing the appearance of the state of the catalyst of the examples and the comparative examples.
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| JP2011000675A JP5731202B2 (en) | 2010-03-08 | 2011-01-05 | Syngas production method and apparatus |
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| JP2017007872A (en) * | 2015-06-17 | 2017-01-12 | エア・ウォーター株式会社 | Synthesis gas production process and apparatus |
| JP6695263B2 (en) * | 2016-11-21 | 2020-05-20 | 東京瓦斯株式会社 | Fuel cell system, control device, and program |
| US11639290B2 (en) * | 2020-06-04 | 2023-05-02 | Saudi Arabian Oil Company | Dry reforming of methane with carbon dioxide at elevated pressure |
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| JP2006056766A (en) * | 2004-08-24 | 2006-03-02 | Chiyoda Corp | Method and reactor for producing synthesis gas |
| US20080263953A1 (en) * | 2004-06-28 | 2008-10-30 | Osaka Gas Co., Ltd. | Reformed Gas Production Method and Reformed Gas Production Apparatus |
| TW200906720A (en) * | 2007-05-24 | 2009-02-16 | Air Water Inc | Carbon monoxide gas generation apparatus and method and carburization atmosphere gas generation apparatus and method |
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| JP4304025B2 (en) * | 2002-12-25 | 2009-07-29 | 大阪瓦斯株式会社 | Operation method of reformed gas production equipment |
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| US20080263953A1 (en) * | 2004-06-28 | 2008-10-30 | Osaka Gas Co., Ltd. | Reformed Gas Production Method and Reformed Gas Production Apparatus |
| JP2006056766A (en) * | 2004-08-24 | 2006-03-02 | Chiyoda Corp | Method and reactor for producing synthesis gas |
| TW200906720A (en) * | 2007-05-24 | 2009-02-16 | Air Water Inc | Carbon monoxide gas generation apparatus and method and carburization atmosphere gas generation apparatus and method |
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| JP5731202B2 (en) | 2015-06-10 |
| TW201202406A (en) | 2012-01-16 |
| WO2011111554A1 (en) | 2011-09-15 |
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