TW294657B - - Google Patents
Download PDFInfo
- Publication number
- TW294657B TW294657B TW083107590A TW83107590A TW294657B TW 294657 B TW294657 B TW 294657B TW 083107590 A TW083107590 A TW 083107590A TW 83107590 A TW83107590 A TW 83107590A TW 294657 B TW294657 B TW 294657B
- Authority
- TW
- Taiwan
- Prior art keywords
- patent application
- catalyst
- item
- stream
- compound
- Prior art date
Links
- 238000006243 chemical reaction Methods 0.000 claims description 132
- 239000003054 catalyst Substances 0.000 claims description 110
- 238000000034 method Methods 0.000 claims description 81
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 67
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 66
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 46
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- -1 alkyl aromatic hydrocarbons Chemical class 0.000 claims description 27
- 238000001514 detection method Methods 0.000 claims description 27
- 230000000694 effects Effects 0.000 claims description 17
- 238000011049 filling Methods 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 6
- 150000003388 sodium compounds Chemical class 0.000 claims 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 210000003298 dental enamel Anatomy 0.000 claims 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910052776 Thorium Inorganic materials 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000007689 inspection Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 230000002079 cooperative effect Effects 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
294657 五、發明説明（ 本發明-般而言係有關於維持極高轉化 _ 〇>了_和極高選擇率（丨㈣丨〇f倉触纽 發明背景 —技藝中已知燒基芳族烴可催化性脱氣而產生缔基芳族 煙’例如$苯成為苯乙缔之轉化反應。先前技藝告知許多 不1的，氫催化劑和反應參數，各具不、同的優點和缺點。. 一般而s，先前技藝告知，於轉化率與選擇率之間、於 =率與催化舰用期之間等等，通常成功和失敗的機會相 若例如，於某些方法中，得到烷基芳族烴高度脱氫之缺 點可能為選擇率之降低，亦即，較高百分比之不良脱氮副 產物。顯然，如果可能的話，同時得到高轉化率和高選擇 率最有利且最不費成本。 催化劑使用期和相關的成本因素，於此等脱氫反應中 ，為另一重要之反應參數。首先為與催化劑本身相關的成 本：雖然催化劑的單位成本可能不大，然而由於所需催化 用量很大以及以環保可接受之法處理用過、被污染的催化 劑之成本，因此催化劑的使用期和將用過的催化劑再生之 能力為商業脱氫反應中具決定性的要素。第二為為了替換 或再生催化劑床，將大的、或許是多階段' 於類似6 〇 〇。〇 之溫度下操作之脱氫反應器關閉相關之成本。除了明顯的 勞力成本，還有於任何時間讓昂貴的設備停線之資本。此 本紙張尺度適用中國國家揉準（CNS } A4规格（2丨0X297公釐） --_-------—^------ΐτ-----0 {請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾準局貞工消費合作社印製 經濟部中央梂準局員工消費合作社印製 A7 _____B7_ 五、發明説明（2 ) 外尚有熱損失加上催化劑替換或再生步驟之成本。甚至更 具意義的為於關閉期間損失生產之成本。 因此，一方面，較佳為將催化劑使用期增加至最長。 但疋，另一方面，於使用時正常的催化劑衰退有讓轉化率 、選擇率、或二者，減少之傾向，而造成反應效率之不良 損失。文獻上對於脱氫催化劑在使用期間典型的衰退現象 有多種可能的解釋，包括催化劑表面之碳化、催化劑填隙 結構之物理崩潰、催化促進劑之喪失等。视催化劑和各種 反應參數而定，一或多種此等機制，或其他尚未被認定之-機制，可能有用。 雖然先前技藝告知欲暫時且只部份恢復催化劑之有效 性而將所用催化劑再生之多種方法，這些方法通常包括停 止脱氫反應、關閉脱氫反應器、或於某些情形下，取出催 化劑作在外再生。此外，這種不時將催化劑再生之反應衝 擊為不良的鋸齒模式產量：轉化率和選擇率間始時相當高 ，但是緩緩地且持續地衰微，到催化劑再生點又恢復相當 高的轉化率和選擇率。但是，隨後立即，催化劑的有效二 又開始衰微。結果，不可能使用習知之催化劑再生法達到 實際上為穩定之南轉化率和高選擇率之反應狀況。 舉例而言，德國專利案第DD 298 353、DD 298 354、Dd 298 355、DD 298 356和DD 298 357號告知於乙苯_至_苯乙 烯脱氫反應中再生催化劑床之3-步驟法，包括：⑴關閉反 應’以蒸汽餵料取代混合蒸汽-乙苯銀料流；（2)接著為加 熱處理步驟；及（3)隨後引入於蒸汽餵料中之钾離子（例如 -------1^------ΪΤ------線 (請先閲讀背面之注意事項再填寫本頁)294657 V. Description of the invention (The present invention generally relates to maintaining extremely high conversions _> _ and _ and very high selectivity (丨 ㈣ 丨 〇f warehouse contact background of invention-known in the art burned aromatic Hydrocarbons can be catalytically degassed to produce alkenyl aromatic smoke, such as the conversion reaction of benzene to styrene. The previous technology informs that many hydrogen catalysts and reaction parameters have different advantages and disadvantages. In general, s, the previous art informed that between conversion rate and selectivity, between = rate and catalytic ship life, etc., the chances of success and failure are usually similar. For example, in some methods, the alkyl aromatic The disadvantage of highly dehydrogenated hydrocarbons may be a reduction in selectivity, that is, a higher percentage of undesirable denitrification by-products. Obviously, it is most advantageous and cost-effective to obtain both high conversion and high selectivity if possible. The service life of the catalyst and related cost factors are another important reaction parameter in these dehydrogenation reactions. The first is the cost associated with the catalyst itself: although the unit cost of the catalyst may not be large, due to the required catalytic The amount is large and the cost of treating the used and contaminated catalyst in an environmentally acceptable method, so the service life of the catalyst and the ability to regenerate the used catalyst are decisive factors in the commercial dehydrogenation reaction. The second is to Replacing or regenerating the catalyst bed, the cost associated with shutting down a large, perhaps multi-stage, dehydrogenation reactor operating at a temperature similar to 6.00. In addition to the obvious labor costs, it can also be expensive at any time. The capital of equipment suspension. This paper standard is applicable to China National Standard (CNS} A4 specification (2 丨 0X297mm) --_--------- ^ ------ lτ ---- -0 (Please read the precautions on the back before filling out this page) Printed by the Ministry of Economic Affairs, Central Bureau of Economic Affairs, Zhengong Consumer Cooperatives Printed by the Ministry of Economic Affairs, Central Bureau of Employment, Employee Consumer Cooperatives A7 _____B7_ V. Description of Invention (2) Heat loss plus the cost of catalyst replacement or regeneration steps. Even more meaningful is the loss of production costs during shutdown. Therefore, on the one hand, it is better to increase the catalyst lifetime to the longest. But on the other hand, When using The decline of the catalyst has a tendency to reduce the conversion rate, selectivity, or both, resulting in an adverse loss of reaction efficiency. There are many possible explanations for the typical decline of the dehydrogenation catalyst during use in the literature, including the surface of the catalyst Carbonization, physical breakdown of the interstitial structure of the catalyst, loss of catalytic promoter, etc. Depending on the catalyst and various reaction parameters, one or more of these mechanisms, or other mechanisms that have not yet been identified, may be useful. Various methods for temporarily and only partially recovering the effectiveness of the catalyst to regenerate the used catalyst. These methods usually include stopping the dehydrogenation reaction, closing the dehydrogenation reactor, or in some cases, removing the catalyst for external regeneration. In addition, this From time to time, the reaction of the catalyst regeneration is impacted into a bad sawtooth mode: the conversion rate and the selection rate are quite high at the beginning, but slowly and continuously decay, and the conversion rate and the selection rate are restored to the catalyst regeneration point. . However, immediately thereafter, the effectiveness of the catalyst began to decline again. As a result, it is impossible to use the conventional catalyst regeneration method to achieve a reaction condition that is practically stable with a high conversion rate and high selectivity. For example, German Patent Nos. DD 298 353, DD 298 354, Dd 298 355, DD 298 356, and DD 298 357 inform the 3-step method of regenerating the catalyst bed in ethylbenzene-to-styrene dehydrogenation, These include: (1) closing the reaction 'replacing the mixed steam-ethylbenzene silver stream with a steam feed; (2) followed by a heat treatment step; and (3) potassium ions subsequently introduced into the steam feed (for example ----- --1 ^ ------ ΪΤ ------ line (please read the notes on the back before filling this page)
經濟部中央標準局®:工消費合作杜印製 ·: A 7 ____ B7 將ΚΟΗ或Κ/〇3汽化）。然而，這些專利文獻無一者告知或 建議任何不干擾反應過程之催化劑再生法。這些德國專利 法會很昂貴、累贊、且產生上面提及的不良之鋸齒模式。 因此先前技藝未能揭示再生或穩定催化劑活性的任何 方法，以於延長時間、高轉化率和高選擇率、不干擾反應 過程下’維持實際上穩定的脱氫反應狀況。先前技藝受限 的這些和其他問題已為本發明之催化劑再生及/或穩定法 和裝置所克服。發明之目的 因此’本發明的主要目的在於提供再生及/或穩定脱 氫催化劑之方法和裝置。 本發明的目的也在於提供秫地再生脱氫催化劑之方法 和裝置。 又’本發明之更明確目的在於提供於不干擾反應過程 下，連續或間歇地再生脱氫催化劑之方法和裝置，以於延 長時間、高轉化率和高選擇率下，維持實際上穩定的脱氣 反應狀況。 本發明之進一步目的在於提供於含有鐵和一或多種驗 金屬化合物之催化劑存在下，將乙苯脱氫成為苯乙晞之改 良方法。 明確地説，本發明的目的在於提供利用連續或間歇地 於反應物流中加入驗金屬.化舍物，以再生及/或穩定含有 鐵和一或多種驗金屬化合物的脆氫催化劑之方法和相關裝 〜5〜 本紙張纽適用中國國家榡準（CNS) A4j^ (2丨0Χ297公着） (請先閲讀背面之注意事哼再填寫本頁) -裝. *1Τ 線Central Bureau of Standards ® of the Ministry of Economic Affairs: Du Printing by Industrial and Consumer Cooperation ·: A 7 ____ B7 vaporize ΚΟΗ or Κ / 〇3). However, none of these patent documents inform or suggest any catalyst regeneration method that does not interfere with the reaction process. These German patent laws can be expensive, tiring, and produce the bad sawtooth pattern mentioned above. Therefore, the prior art fails to reveal any method for regenerating or stabilizing the activity of the catalyst to maintain a dehydrogenation reaction condition that is practically stable under extended time, high conversion rate and high selectivity without disturbing the reaction process. These and other problems with prior art limitations have been overcome by the catalyst regeneration and / or stabilization method and apparatus of the present invention. Object of the Invention Therefore, the main object of the present invention is to provide a method and apparatus for regenerating and / or stabilizing the dehydrogenation catalyst. The object of the present invention is also to provide a method and an apparatus for regenerating a dehydrogenation catalyst. Also, the more specific purpose of the present invention is to provide a method and an apparatus for continuously or intermittently regenerating a dehydrogenation catalyst without interfering with the reaction process, so as to maintain a practically stable desorption under extended time, high conversion rate and high selectivity Gas reaction status. A further object of the present invention is to provide an improved method for dehydrogenating ethylbenzene to phenethylbenzene in the presence of a catalyst containing iron and one or more metal detection compounds. Specifically, the object of the present invention is to provide methods and related to the use of continuous or intermittent addition of metal detection compounds in the reaction stream to regenerate and / or stabilize the brittle hydrogen catalyst containing iron and one or more metal detection compounds Install ~ 5 ~ This paper button is suitable for China National Standard (CNS) A4j ^ (2 丨 0Χ297 public) (please read the notes on the back and fill in this page) -install. * 1Τ line
A7 ： 本!1 B B7_補免_ 五、發明説明（） 置。 本發明之其他目的部份將出現於下文，部份由下文明 顯可見。本發明因此係包含有關幾個步驟之方法、反應和 裝置、及一或多個此等步驟與各個其他步驟及下面細節揭 示内容例舉的裝置之關係和順序、和於申請專利範圍所示 之申請範圍。 發明摘要 本發明之脱氫催化劑再生及/或穩定法包括於繼續進‘ •行脱氫反應下，連續或間歇地於反應物餵料流中加入有效 量的驗金屬化合物之步驟。本發明的方法也包括逐漸增加 反應帶溫度之步驟。本發明的方法可用於，例如於乙苯成 為苯乙烯之催化劑性脱氫反應中，達到高轉化率和高選擇 率之實際上穩定的反應狀況。 圖式簡單説明 圖1為本發明方法和裝置一具體實例之代表性略圖。 圖2説明進行本發明鹼金屬化合物添加步驟之較佳方 法和相關裝置。 經濟部中夹標苹局只工消费合作杜印繁 ^^^1« m^i —^^pn nvt— ti 1111 f —ν^ϋ mu ^m· 一°J_ (請先閱讀背面之注意事項再填寫本頁) 圖3説明進行本發明鹼金屬化合物添加步驟之替代方 法和相關裝置。 較佳具體實例之詳細說明 本發明方法廣泛地包括再生及/或穩定用於將境基芳 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 經濟部中央梂準局貝工消費合作社印製 銘 S7 _^___ 五、發明説明（5 ) 族烴催化性脱氫以製得特定需要的烯基芳族烴的脱氫催化 劑之活性。此等脱氫催化劑為技藝中一般悉知且為市售可 得。通常，此等催化性脱氫反應係於範圍在約400。(：至約700 °(：之溫度下，較佳為於約5〇〇°C至700 °C間，將含有烷基芳 族烴和蒸汽之預先加熱之餵料流，與特定的脱氫催化劑接 觸進行之。反應可於具有固定催化劑床或流化床之單一或 多階反應器中進行。起始烷基芳族烴、脱氫催化劑、反應 溫度和餵料流中烷基芳族烴對蒸汽的比例之選擇，會部份 影響生成的埽基芳族烴以及轉化過程的效率和選擇性。 特別是，使用前面提及的方法，與含有鐵和至少一種 鹼金屬化合物之催化劑接觸，將乙苯轉化為苯乙缔。例如 ，乙苯-至-苯乙烯之轉化反應可於從約500 °C至约700 °C之 反應溫度範圍内，較佳為於從約550°C至約650°C，和於從 約3至約2〇psia，較佳為從約5至约9psia之壓力下予以進行 。反應物流中蒸汽-對-烴之比可從約0.6:1至約3:1蒸汽對乙 苯重量比之範圍内，較佳為約1.0:1至約2·〇:1蒸汽對乙苯重 量比。空間速度每公斤催化劑每小時可從約〇·2至約1_2公 斤乙苯之範圍内。 以新的催化劑開始乙苯-至—苯乙烯之轉化反應，啓動 後典型地為持續約3-45天之最初調整期，其特點為高起始 活性，隨後迅速地失去活性。例如，於最初調整期間，乙 苯對苯乙烯之總轉化率可能跌落至約55莫耳。/。以下，苯乙 缔選擇率可能跌落至約93莫耳。/。以下。其後於習知乙苯—至一 苯乙烯之轉化反應中，催化劑活性繼續下降，雖然其速率 裝------訂-----—線 (請先閱讀背面之注意事項再填寫本頁)A7: This! 1 B B7_Compensation and Exemption_ Fifth, the invention description (). Other objects of the present invention will appear below, some of which are clearly visible from the next civilization. The present invention therefore includes methods, reactions, and devices related to several steps, and the relationship and sequence of one or more of these steps with various other steps and the devices exemplified in the detailed disclosure below, and as shown in the scope of the patent application Application scope. SUMMARY OF THE INVENTION The dehydrogenation catalyst regeneration and / or stabilization method of the present invention includes the step of continuously and intermittently adding an effective amount of a metal detection compound to the reactant feed stream while continuing the dehydrogenation reaction. The method of the present invention also includes the step of gradually increasing the temperature of the reaction zone. The method of the present invention can be used, for example, in a catalytic dehydrogenation reaction of ethylbenzene to styrene to achieve a practically stable reaction condition with high conversion and high selectivity. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a representative sketch of a specific example of the method and apparatus of the present invention. Figure 2 illustrates a preferred method and related apparatus for performing the alkali metal compound addition step of the present invention. The Ministry of Economic Affairs, the Ministry of Economic Affairs, the Ping An Bureau only works on consumer cooperation Du Yinfan ^^^ 1 «m ^ i — ^^ pn nvt— ti 1111 f —ν ^ ϋ mu ^ m · 一 ° J_ (Please read the notes on the back first (Fill in this page again) Figure 3 illustrates an alternative method and related apparatus for performing the alkali metal compound addition step of the present invention. Detailed description of preferred specific examples The method of the present invention broadly includes recycling and / or stabilization for the application of Jingji Fangben paper to the Chinese National Standard (CNS) A4 specification (210X 297 mm). The cooperative printed the inscription S7 _ ^ ___ V. Description of the invention (5) The activity of the dehydrogenation catalyst for the catalytic dehydrogenation of group hydrocarbons to obtain specific needs of alkenyl aromatic hydrocarbons. These dehydrogenation catalysts are generally known in the art and are commercially available. Generally, these catalytic dehydrogenation reactions are in the range of about 400. (: To a temperature of about 700 ° (: preferably at a temperature of about 500 ° C to 700 ° C, a pre-heated feed stream containing alkyl aromatic hydrocarbons and steam is dehydrogenated The catalyst is carried out in contact. The reaction can be carried out in a single or multi-stage reactor with a fixed catalyst bed or fluidized bed. Starting alkyl aromatic hydrocarbons, dehydrogenation catalyst, reaction temperature and alkyl aromatic hydrocarbons in the feed stream The choice of the ratio of steam will partially affect the efficiency and selectivity of the produced quaternary aromatic hydrocarbons and the conversion process. In particular, using the aforementioned method, contact with a catalyst containing iron and at least one alkali metal compound, Convert ethylbenzene to styrene. For example, the conversion of ethylbenzene-to-styrene can range from about 500 ° C to about 700 ° C, preferably from about 550 ° C to about 650 ° C, and at a pressure of from about 3 to about 20 psia, preferably from about 5 to about 9 psia. The steam-to-hydrocarbon ratio in the reaction stream may be from about 0.6: 1 to about 3: 1 Within the range of steam to ethylbenzene weight ratio, preferably about 1.0: 1 to about 2.0: 1 steam to ethylbenzene weight ratio. The speed per kilogram of catalyst can range from about 0.2 to about 1 to 2 kilograms of ethylbenzene per hour. The conversion of ethylbenzene to styrene is started with a new catalyst, which typically lasts about 3 to 45 days after startup During the initial adjustment period, it is characterized by high initial activity, and then quickly loses activity. For example, during the initial adjustment period, the total conversion rate of ethylbenzene to styrene may fall to about 55 moles. The selectivity may drop to about 93 mol./. Below. Later in the conventional conversion reaction of ethylbenzene-to-styrene, the catalyst activity continued to decrease, although its rate was set to -------- --- line (please read the notes on the back before filling this page)
經濟部中央樓準局負工消費合作社印衆 A7 * ________ B7 五 '發明説明 --- 較最初調整期間慢些。於多階反應器中，乙苯至苯乙缔之 轉f率每—階段下降約三分之一，例如，於最初調整期間 從約3〇—36莫耳。/。至约2〇—24莫耳。/。，然後繼續以較慢之速 二下降。於此法中最初調整期終了通常可被熟悉此項技藝 者從轉化率對時間作圖直線斜率變平之點識別出來。如前 2述，先前技藝對於催化劑活性之逐漸衰微已建議許多可 月b的，釋，惟無任一機制可充分解釋此現像。 f淪其解釋為何，超過最初調整期後持續之反應衰微 導致許多問題和缺點。第―，轉化反應之效率減少。未經 f應的乙苯必須與產物流的其他成分分離以供循環使用。 笨^烯同樣地必須與未經反應之乙苯及其他反應產物分離 第了，具有苯乙烯、乙苯和各種副產物比例相當一定 的相當均勻之產物流，由於反應衰微而成為組成不斷改變 的產物流。第三，於某些點，轉化率或苯乙烯之選擇率或 一者下降得相當低，使得反應不再經濟可行。此時，最好 關閉反應和以習知方法置換催化劑或將催化劑再生。 維持乙苯成為苯乙烯的轉化率之—技巧為提升反應溫 度，可以，例如，利用增加反應物流之溫度或利用加熱至 反應室而達成。反應溫度可緩緩且實際上持續地增加或可 不時地加溫。此等反應溫度增加之影響為增加反應速率以 彌補催化劑活性之持'續哀微。但是，這種溫度提升技術之 使用受到相當大的限制。特別是，在某溫度以上，即接近 催化劑或設備的機械溫度極限。超過此點，進一步的溫度 增加將導致催化劑物理結構之降解和設備完整性之降解。 本紙涑尺度速用中國國家棣準（CNS ) Α4说格（210Χ297公釐） -------丨^------ΐτ-----，.線· (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作杜印製 、發明説明（ 因此，在接近前述極限時，最好關閉反應和以習知方法置 換催化劑或將催化劑再生。此等溫度提升技術對催化劑使 用期雖然有些延長而可被利用（例如，經由持續或少量、 時時之溫度增加）以於有限的時間内維持相當一定的乙苯 轉化率，惟其本身由於所述理由而使其利用性受到限制。 、對照之下，本發明之方法可以恢復及/或穩定催化劑 活性，結果催化劑使用期之延長遠超過習知方法所能達成 者三更特別地’本發明之方法可以恢復脱氫催化劑之活性 至實際上與最初調整期終了時—樣高的轉化率和選擇率。· 於延長時間内’本發明之方法也可以穩定催化劑活性於一 樣高的轉化率和選擇率，超過習知方法所能達成者。本發 明之方法也可與前述溫度提升技術搭配使用〃得到更為 加催化劑使用期或增加乙苯轉化率之附加利益。本發明方 if”含有烷基芳族烴之反應物流中連續或間歇 心二(其里足以再生、穩定、或加強脱氫催化劑 健1。^屬化合物之步驟’111而恢復及維持高轉化率和 右=又中所用”維持"―詞意欲解釋為，.保持於修復、 狀態丄於延長的時間(例如許多月或年)内 綠祕么思3哀< 。方法特別用於有關含有鐵和至少一 種，金屬化合物的脱氫催化劑之再生及/或穩定。此等脱 ^催化劑為技藝中悉知，其中有些為市售可得，包括：得 MASF公司之S6-20、S6都S6说系列；得自⑽_ Μ— ==晴，L.P.之cmos、c_〇15、讓和c_〇35系列；及 侍自umted Catalysts，lnc之匕64和㈣系列（包括下文中實 + ( CNS ) ( 210^7^- -------—裝------訂-----ά, (請先W讀背面之注意事項再填寫本頁)Yinzhong A7 * ________ B7 Five 'Invention Description --- Slower than the initial adjustment period. In a multi-stage reactor, the conversion rate of ethylbenzene to styrene decreases by about one third per stage, for example, from about 30 to 36 moles during the initial adjustment period. /. To about 20-40 moles. /. , And then continue to descend at a slower rate. The end of the initial adjustment period in this method can usually be identified by the person skilled in the art from the point where the slope of the straight line of the conversion rate versus time is flattened. As mentioned in the previous two, the prior art has suggested many explanations for the gradual decline of catalyst activity, but there is no mechanism to fully explain this phenomenon. f explains why the continued decline of the response beyond the initial adjustment period has caused many problems and shortcomings. First, the efficiency of the conversion reaction is reduced. Untreated ethylbenzene must be separated from other components of the product stream for recycling. The styrene must also be separated from the unreacted ethylbenzene and other reaction products. It has a fairly uniform product flow with a certain ratio of styrene, ethylbenzene and various by-products. It becomes a constantly changing composition due to the decay of the reaction. Product stream. Thirdly, at some point, the conversion rate or the selectivity of styrene or one of them drops very low, making the reaction no longer economically feasible. At this time, it is better to shut down the reaction and replace or regenerate the catalyst by conventional methods. Maintaining the conversion rate of ethylbenzene to styrene-techniques for increasing the reaction temperature can be achieved, for example, by increasing the temperature of the reaction stream or by heating to the reaction chamber. The reaction temperature may increase slowly and actually continuously or may be warmed from time to time. The effect of these increased reaction temperatures is to increase the reaction rate to make up for the continued activity of the catalyst. However, the use of this temperature raising technique is quite limited. In particular, above a certain temperature, it is close to the mechanical temperature limit of the catalyst or equipment. Beyond this point, further temperature increase will lead to degradation of catalyst physical structure and degradation of equipment integrity. This paper uses the Chinese National Standard (CNS) Α4 saying grid (210Χ297mm) ------- 丨 ^ ------ lτ -----, .line (please read the back first Please pay attention to this page and then fill out this page.) Printed and invented the description of the employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs. Although the promotion technology can extend the service life of the catalyst somewhat, it can be utilized (for example, through continuous or small-scale, constant temperature increase) to maintain a certain conversion rate of ethylbenzene within a limited period of time. Its availability is limited. In contrast, the method of the present invention can restore and / or stabilize the catalyst activity, and as a result, the use of the catalyst is extended far beyond what can be achieved by the conventional method. More specifically, the method of the present invention can be restored The activity of the dehydrogenation catalyst is actually as high as the conversion rate and selectivity at the end of the initial adjustment period. · For an extended period of time, the method of the present invention can also stabilize the catalyst activity at the same high The conversion rate and selectivity are beyond what can be achieved by conventional methods. The method of the present invention can also be used in conjunction with the aforementioned temperature increase technology to obtain additional benefits of more catalyst life or increased ethylbenzene conversion rate. "The reaction stream containing alkyl aromatic hydrocarbons is continuous or intermittent (there is sufficient to regenerate, stabilize, or enhance the dehydrogenation catalyst. ^ Belongs to compound step '111 while recovering and maintaining a high conversion rate and The term "maintenance" used in the article is intended to be interpreted as, "maintained in a repaired state, for a prolonged period of time (for example, many months or years)". The method is especially used for iron and at least one , The regeneration and / or stabilization of metal compound dehydrogenation catalysts. These desulfurization catalysts are well known in the art, and some of them are commercially available, including: S6-20 and S6 S6 series from MASF Corporation; Since ⑽_ Μ — == sunny, LP's cmos, c_〇15, let and c_〇35 series; and servants from umted Catalysts, lnc's dagger 64 and ㈣ series (including the following real + (CNS)) (210 ^ 7 ^--------— install ------ order ----- ά, (Please W first Note to fill out the back of this page)
經濟部中央梂準局貝工消費合作杜印製 例1-4所用足G-84C催化劑）。這些催化劑典型地么 Fe203 ’ 5_3G%K2Q ’及其他促進劑。所有此等4請％ 化劑均被視為屬於本發明之範圍内。 、負似之催 本發明之方法可使用於幾乎任何烷基芳族蛵 晞基芳族烴之催化性脱氫反應。為了制特定為對應 芳族烴，垸基芳族烴、催化劑和反應條件㈣=浠^ 藝中一般悉知且，於任何情形下，與選擇和例二， 。本發明方法特別用於將乙苯轉化為苯乙烯之反 催化劑之再生及/或穩定。 ％中肮虱 圖1為一流程圖，概略地説明本發明方法之—— 例，其中係將驗金屬化合物加到進來的銀料流以 階反應器的部份經轉化之反應物流中。為了討論圖1 使 用••餵料流"和’’部份經轉化之反應物流.，以助於識別化反 應之特定階段，於本説明文其他地方，這些名詞被視為一 般名詞且可互換。於圖彳中，進來的餵料流1可為含有烷基 芳族烴，例如乙苯之餵料，進來的餵料流2可為^汽二二 圖1所示，有效量之鹼金屬化合物係連續或間歇地利用鹼 金屬供應裝置46加到餵料流2中。替代地，鹼金屬化合物 可加到餵料流1中。餵料流彳和2 ,包括任何鹼金屬化合物 ，組合成反應物流3導向第一階反應器50(其中裝填適當之 脱虱催化劑）之入口。替代地，驗金屬化合物可於餵料流， 和2組合成反應物流3後、於第一階反應器50之前加入。部 份燒基芳族烴之轉化，例如乙苯成為苯乙晞，發生於反應 器50。 本紙張尺度適用中國國家襟準（CNS) A4規格（210x297公釐） I I n 裝 I — ^---1 —^-線 (請先閱讀背面之注意事項再填寫本頁) A7 B7 394657 五、發明説明（9 從反應器50出來之部份經轉化之反應物流或出口流4 接著通過再加熱器52以恢復於反應器5〇之熱損失，再獲得 適當的反應溫度。來自驗金屬供應裝置66的補充驗金屬化 合物連續或間歇地加到從再加熱器52出來的部份經轉化之 反應物流5中(於反應物流5被導向第二階反應器54入口之前） 。替代地，補充鹼金屬化合物可在從反應器5〇出來的部份 經轉化之反應物流4進入再加熱器52之前，加入其中。反 應器54中也裝填適當的脱氫催化劑，於其内發生烷基芳族 fe進一步之轉化。對熟悉此項技藝者顯而易見地，可使用 附加之下游反應器，例如第三或第四階反應器，其中各裝 %適當的催化劑，以得到燒基芳族煙更進一步之轉化。根 據本發明方法於反應物流中鹼金屬化合物之添加可方便地 於多階反應器中一些或所有反應器之間進行。 如圖1所示’本發明之裝置可便利地包含檢測裝置， 例如分別與反應物流4和6相關之檢測裝置42和62，以檢測 來自任何一或多個反應器出口處出口流之化學成分。檢測 裝置也可便利地與活化裝置（例如分別為電線44和64)連結 ’以對位於標的反應器（即分別為反應器5〇和54)上游之鹼 金屬化合物供應裝置（例如分別為泵或注射裝置46和66)作 信·號和活化之。 檢測裝置可經由習知技術改裝，每當來自標的反應器 的出口流之轉化率或選擇率下降至預定標準以下（表示反 應器中催化劑活性降解）時’即對鹼金屬化合物供應裝置 送出信號。驗金屬化合物供應裝置被得自相關檢測裝置之 -------丨$------tr----- -.ii (請先閣讀背面之注意事項再填寫本育) 經濟部中央標準局貝工消費合作社印袈 11 294657(Made by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs, Shelley, Consumer Cooperation, Co., Ltd. Du Yin made the G-84C catalyst used in Examples 1-4). These catalysts are typically Fe203 '5_3G% K2Q' and other promoters. All these chemical additives are considered to be within the scope of the present invention. 4. Negative resemblance The method of the present invention can be used for the catalytic dehydrogenation of almost any alkyl aromatic chrysanthemum aromatic hydrocarbon. In order to prepare specific aromatic hydrocarbons, alkyl aromatic hydrocarbons, catalysts and reaction conditions are generally known in the art and, in any case, are related to selection and example two. The method of the invention is particularly useful for the regeneration and / or stabilization of counter catalysts for the conversion of ethylbenzene to styrene. Fig. 1 is a flow chart schematically illustrating the method of the present invention-for example, in which a metal detection compound is added to a part of the converted reaction stream of the incoming silver stream to the reactor. To discuss the use of Figure 1 • feed stream " and ”part of the converted reaction stream. To help identify specific stages of the reaction, these terms are considered as general nouns and can be used elsewhere in this description exchange. In FIG. 2, the incoming feed stream 1 may be a feed containing alkyl aromatic hydrocarbons, such as ethylbenzene, and the incoming feed stream 2 may be steam 2 as shown in FIG. 1, an effective amount of an alkali metal compound It is added to the feed stream 2 continuously or intermittently using an alkali metal supply device 46. Alternatively, alkali metal compounds may be added to feed stream 1. The feed stream 2 and 2, including any alkali metal compound, are combined to form a reaction stream 3 which is directed to the inlet of the first-stage reactor 50 (which is filled with a suitable de-lice catalyst). Alternatively, the metal detection compound may be added after the feed stream, and 2 are combined into the reaction stream 3, and before the first stage reactor 50. The conversion of some of the burned aromatic hydrocarbons, such as ethylbenzene to phenylethylbenzene, occurs in the reactor 50. The size of this paper is applicable to China National Standard (CNS) A4 (210x297 mm) II n Pack I — ^ --- 1 — ^-line (please read the precautions on the back before filling this page) A7 B7 394657 V. Description of the invention (9 The part of the converted reaction stream or outlet stream 4 coming out of the reactor 50 is then passed through the reheater 52 to recover the heat loss in the reactor 50, and then obtain the appropriate reaction temperature. From the metal test supply device The supplementary metal test compound of 66 is added continuously or intermittently to the converted reaction stream 5 from the reheater 52 (before the reaction stream 5 is directed to the inlet of the second-stage reactor 54). The metal compound may be added to the reheater 52 before the converted reactant stream 4 from the reactor 50. The reactor 54 is also filled with a suitable dehydrogenation catalyst, in which alkyl aromatic fe occurs Further conversion. It is obvious to those skilled in the art that additional downstream reactors can be used, such as third or fourth-stage reactors, each of which is equipped with a suitable catalyst to obtain burnt aromatic smoke. Conversion. The addition of alkali metal compounds in the reaction stream according to the method of the present invention can be conveniently carried out between some or all of the reactors in a multi-stage reactor. As shown in FIG. 1, the device of the present invention can conveniently include a detection device, For example, detection devices 42 and 62 associated with the reactant streams 4 and 6, respectively, to detect the chemical composition from the outlet stream at any one or more reactor outlets. The detection device can also be conveniently connected to the activation device (eg, wires 44 and 64) Connection 'to signal and activate the alkali metal compound supply device (such as pump or injection device 46 and 66, respectively) located upstream of the target reactor (ie, reactor 50 and 54 respectively). It can be modified by conventional technology, and whenever the conversion rate or selectivity of the outlet stream from the target reactor drops below a predetermined standard (indicating the degradation of catalyst activity in the reactor), a signal is sent to the alkali metal compound supply device. The compound supply device is obtained from the relevant detection device ------- 丨 $ ------ tr ----- -.ii (Please read the precautions on the back before filling in this education) Ministry of Economy Central Bureau of Standards HIGHLAND consumer cooperatives Indian Buddhist monk's robe 11,294,657
、發明說明（1〇 經濟部中央梯窣局貝工消費合作杜印製 物至相先驗金屬化合 化率或選擇率跌落：== 時:於活化後連續供應驗金屬化合物-段預定的 催丄相關檢測裝置之另—信號告知標的反應器之 催化劑雜已恢復關需活性標準為止。 人你述自動、間歇加入系外，將預定量之驗金屬化 彳各餵料流或反應物流中之替代法也在本發明. 時S，或，替代地，以預定量之鹼金屬化合物於預定 歇^間隔加入。此可與一或多個反應器出口流之連續或間 * X測組合。收到任何反應器中催化劑降解之信號後，從 私的反應器上游增加鹼金屬化合物至餵料流或反應物流之 、恭加~7以手工活化之。驗金屬化合物加入之增加率可於限 定之時間内進行，至恢復所需催化劑活性標準為止，否則 仍維持於新的、較高之增加率。 圖2概括地略為詳細地説明根據本發明將鹼金屬化合 物加到餵料流或反應物流之一較佳方法和相關裝置。圖2 中之導管Ί0含有物流η並將其導向如箭頭所示含有脱氫催 化劑的反應器之方向。物流U可代表，例如，如圖彳所示 之餵料流1或2、合併之反應物流3、或部份經轉化之反應 物流4和5。鹼金屬化合物呈水溶液型22，經由穿過導管1〇 壁上小孔安裝的注射管2〇出口端的注射裝置24傳送，連續 或間歇地加至物流柁。於注射管2〇出口端下游之物流14， 12' 本紙張尺度適用中國國( CNS ) A4AUM21〇X297^* ) ------------^------1T------ (請先«讀背面之注意事項再填寫本頁) A7 B7 ------- 五、發明説明（11 ) 已與根據本發明的驗金屬化合物混合之銀料流或反 圖3概括地説明根據本發明 流或反應物流之替代方法和相關^金屬化合物，到餵料 反心之向如箭頭12和14所示含有脱氫催化劑的 如圖1所示之銀料 導二口進瓦3、或部份緩轉化之反應物流4和5 導f 10進一步地包含蒸汽可進入 體或液體物質之相連容器3〇。呈可裝盛固· 化合物可依需要，經由餵料32，之紅驗金屬 中。容器30下游之物流14，代表已與=過的物流 化合物混合之銀料流或反應物流。、 發明的驗金屬 _進=!方法有用之驗金屬化合物包括所有梅 來源乂驗金屬離子。本發明所用之"驗金屬" 乂惟:侷限於’卸、鋼、經和週期表|A族金屬；= ^過者’例如·铯。然而，考慮成本後通常 不 3化合物之選擇。在某些應財，週期表IIA族之曰=甲 例如錢、料）也可使用。it當驗金屬化合物二，、（ ^與例行f驗相關。至於乙苯成為苯㈣反被= 佳之鹼金屬化合物為鉀化合物，特別是選自含〔^愿，較 氫氧化鉀和碳酸鉀基群中之一或多種化合物:=化鉀' 多種鹼金屬化合物混合物也在本發明之範圍内。兩種或 離子，例如氣離子，典型地會毒害脱氫催化由於鹵素 A ’因此驗 •13- &紙張尺度朝中關家料（CNS ) A4祕（21GX297公釐 I^訂-----一-線 (請先閲讀背面之注意事頊再填寫本頁} 經濟部中央樣準局員工消費合作社印製 經濟部中央樣準局貝工消f合作社印製 A7 ---—------__ B7 五、發明説明（12 ) ' ---- 金屬化合物例如氯化鉀通常避免使用。 根據本發明，加到餵料流或反應物流的鹼金屬化合物 之量，視催化劑、烷基芳族烴、反應條件和鹼金屬化^物 本身而定。為了使反應之進行最適當，足以維持高轉化率 和選擇率之反應物流中鹼金屬化合物之有效添加量或有效 添加率可利用例行實驗決定之。一般而言，頃已發現有效 量之鹼金屬化合物於代表性時間内平均含有反應物流之從 約〇.〇1至約100百萬分點重量比之鹼金屬化合物，較佳為 從約〇_1〇至約1〇百萬分點重量比。本文所用的代表性時間-内意指不再添加鹼金屬化合物而維持高轉化率和選擇率之 期間。於此時間内改變鹼金屬化合物之量以恢復或維持最 適反應之進行也屬本發明之範圍内。 鹼金屬化合物可連續或間歇地及，如果係間歇地，則 依規則或不規則間隔，加到反應物流中。無論鹼金屬化合 物係連續或間歇地加入，其添加量及，於間歇添加之情形 下，間隔之選定，必須確保有效量之添加足以恢復或推持 所需之高轉化率和選擇率。通常，此等量於代表性時間内 平均含有反應物流之從約0 _ 01至约1 〇〇百萬分點重量比之驗 金屬化合物。 鹼金屬化合物之添加至反應物流可以多種方法達成。 此添加法之一為將鹼金屬化合物呈乾燥、固體、粉末型加 到反應物流中。替代地，固體塊或含有呈固體、液體或溶 液型鹼金屬化合物之容器可置於經加熱反應物流之流程中 ’如圖3所示’令其緩緩地汽化和進入通過的物流中。另 〜14〜 本紙張尺度適用中國國家梂準（CNS ) Α4規格（2丨〇>< 297公釐） (請先聞讀背面之注意事項再填寫本頁) -裝 丨線 五、發明説明（13 A7 B7 經濟部中央搮準局貝工消費合作社印製 二特佳（添加法係將呈水溶液型之驗金屬化合物加到反爲 中，舉例而言如上面有關圖2之所述。呈水溶液型： =化合物之添加法由於容易處理和可使反應自動化，如 有關圖1之所述，通常可能為本發明較佳之商業應用。另 一添加法為將呈液體型之鹼金屬化合物注入反應物流中； 另一添加法為將鹼金屬化合物預先汽化並將蒸汽注入反應 物流中。 '參照下列實例和試驗數據，對本發明方法可更為瞭解 ,惟其只供説明用而不對本發明之範圍和施行有所侷限。-實例1 將莫耳比率為12比1和流速為825克/小時之蒸汽和乙苯 引入以1吋目錄40(SChedU|e 40)不銹鋼管構成的反應器中， 並於一 8區電烤箱中加熱。將United Catalysts’ |nc製造、名 稱為G-84C、總重390克之催化劑分四段裝填於反應器中。 反應器中以惰性鋁氧球填塞於第一段催化劑上面、各段催 化劑之間和第四段催化劑下方。以250 °C之溫度進入反應 器之反應混合液在進入第一段催化劑時預先加熱至598。匸 。四段催化劑之平均溫度維持於594 °C上下彳内。反應 器·出口處維持於常壓。如下面表1所示，在上物流時間854 和1298小時之間觀察到催化劑之失活。此期間由於乙苯轉 化率下降’苯乙缔選擇率稍微增加。於1 31 〇小時，關閉 測試單元’將裝填5.4克ACS級KOH之不銹鋼容器置於鋁氧 上方。俟反應器再啓動後’少量KOH繼續汽化而被反應器 衣紙張尺度適用中國國家棟準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) -裝_3. Description of the invention (10. The Centralized Ladder Bureau of the Ministry of Economic Affairs, the shellfish consumer cooperation, and the phase-to-phase prior metal compounding rate or selectivity drop: == time: continuous supply of metal test compound after activation-scheduled reminder In addition to the related detection devices-the signal informs that the catalyst in the target reactor has been restored to the point where the activity standard is required. It is automatically and intermittently added to the system, and a predetermined amount of metallization is fed into each feed stream or reaction stream. Alternative methods are also present in the present invention. At the time S, or, alternatively, a predetermined amount of alkali metal compound is added at predetermined intervals. This can be combined with continuous or intermittent measurement of one or more reactor outlet streams. After the signal of catalyst degradation in any reactor, add alkali metal compound from the upstream of the private reactor to the feed stream or reaction stream, and add ~ 7 to manually activate it. The increase rate of the addition of metal test compound can be limited Within a period of time until the required standard of catalyst activity is restored, otherwise it will remain at a new, higher rate of increase. Figure 2 outlines a little more detailed description of the addition of alkali metal compounds to the Feed stream or reactant stream is one of the preferred methods and related equipment. Conduit Ί0 in Fig. 2 contains stream η and leads it to the direction of the reactor containing the dehydrogenation catalyst as indicated by the arrow. Stream U can represent, for example, Figure 1 shows feed stream 1 or 2, combined reaction stream 3, or partially converted reaction streams 4 and 5. The alkali metal compound is in the form of an aqueous solution 22, which is installed through a small hole in the wall of the conduit 10 The injection device 24 at the outlet end of the injection tube 20 is conveyed and added to the stream continuously or intermittently. The stream 14, 12 'downstream of the outlet end of the injection tube 20 This paper size is applicable to China (CNS) A4AUM21〇X297 ^ *)- ----------- ^ ------ 1T ------ (please first «read the notes on the back and then fill out this page) A7 B7 ------- V. Description of the invention (11) The silver stream or reverse flow which has been mixed with the metal detection compound according to the present invention generally illustrates an alternative method and related metal flow according to the present invention or related to the metal compound. Arrows 12 and 14 show a silver material containing a dehydrogenation catalyst as shown in Figure 1 through two inlets into the tile 3, or part of the slowly converted reaction stream 4 and 5 lead f 10 further contain a vapour-enterable connected container 3 of body or liquid material. It can be filled with Shenggu. The compound can be fed into 32, red metal according to need. The stream 14 downstream of the container 30 represents a silver stream or reaction stream that has been mixed with the stream compound. Invented metal detection _ 进 =! Method useful metal detection compounds include all plum sources and metal detection ions. The " metal detection " used in the present invention is limited to: "discharge, steel, warp, and periodic table | Group A metals; = ^^ 的", for example, cesium. However, considering the cost, it is usually not the choice of 3 compounds. In some financial applications, the IIA of the periodic table = A (for example, money, materials) can also be used. It is a metal compound II, and (^ is related to the routine f test. As for ethylbenzene to become benzene, anti-quilt = the preferred alkali metal compound is a potassium compound, especially selected from the group consisting of potassium hydroxide and potassium carbonate. One or more compounds in the group: = potassium ', a mixture of various alkali metal compounds is also within the scope of the present invention. Two kinds of ions, such as gas ions, typically poison the dehydrogenation catalyst due to halogen A'. -& Paper-scale North Korea House Material (CNS) A4 Secret (21GX297mm I ^ Order ----- One-line (please read the precautions on the back first and then fill out this page) Ministry of Economic Affairs Central Sample Bureau Employee consumption cooperatives printed A7 -----------__ B7 printed by Beigongxiao F Cooperative of the Ministry of Economic Affairs of the Central Bureau of Economics of the Ministry of Economy. 5. Description of invention (12) '---- Metal compounds such as potassium chloride are usually Avoid use. According to the present invention, the amount of alkali metal compound added to the feed stream or reaction stream depends on the catalyst, alkyl aromatic hydrocarbon, reaction conditions, and alkali metal compound itself. In order to make the reaction proceed most appropriately , Sufficient to maintain a high conversion rate and selectivity of alkali metallization in the reaction stream The effective addition amount or effective addition rate of a substance can be determined by routine experiment. Generally speaking, it has been found that an effective amount of an alkali metal compound contains an average of from about 0.01 to about 100 of the reaction stream in a representative time The alkali metal compound with a 10,000 point weight ratio is preferably from about 〇10 to about 10 million point weight ratio. The representative time used herein means that no additional alkali metal compound is added to maintain high conversion The period of the rate and selectivity. It is within the scope of the invention to change the amount of the alkali metal compound during this time to recover or maintain the optimal reaction. The alkali metal compound can be continuous or intermittent and, if it is intermittent, the Regular or irregular intervals are added to the reaction stream. Whether the alkali metal compound is added continuously or intermittently, the amount of addition and, in the case of intermittent addition, the interval must be selected to ensure that the effective amount of addition is sufficient to restore or promote The required high conversion rate and selectivity. Generally, these amounts contain an average of the reactant stream from about 0 _ 01 to about 100 million point weight ratio of the assay in a representative time Compounds. The addition of alkali metal compounds to the reaction stream can be achieved in a variety of ways. One of the addition methods is to add the alkali metal compound to the reaction stream in a dry, solid, or powder form. Alternatively, the solid block may contain solid, liquid or The container of the solution type alkali metal compound can be placed in the flow of the heated reaction stream 'as shown in Figure 3' so that it slowly vaporizes and enters the passing stream. Another ~ 14 ~ This paper size is applicable to the Chinese national standards ( CNS) Α4 specification (2 丨 〇 < 297mm) (Please read the precautions on the back and then fill out this page) -Installation 丨 Five, description of invention (13 A7 B7 Ministry of Economic Affairs Central Bureau of Industry and Commerce Printed by the Consumer Cooperatives, Ertejia (addition method is to add an aqueous solution-type metal detection compound to the reverse, for example, as described above in relation to Figure 2). In the form of an aqueous solution: = The addition method of the compound is easy to handle and can automate the reaction. As described in relation to Fig. 1, it may generally be a better commercial application of the present invention. Another addition method is to inject an alkali metal compound in a liquid form into the reaction stream; another addition method is to pre-evaporate the alkali metal compound and inject steam into the reaction stream. 'Refer to the following examples and test data to understand the method of the present invention better, but it is for illustration only and does not limit the scope and implementation of the present invention. -Example 1 Steam and ethylbenzene with a molar ratio of 12 to 1 and a flow rate of 825 g / h were introduced into a reactor composed of 1 inch catalog 40 (SChedU | e 40) stainless steel tubes and placed in an 8-zone electric oven Medium heating. A catalyst made by United Catalysts || nc, named G-84C, with a total weight of 390 grams was loaded into the reactor in four stages. The reactor was packed with inert aluminum oxide spheres above the first stage catalyst, between each stage catalyst and below the fourth stage catalyst. The reaction mixture entering the reactor at a temperature of 250 ° C is preheated to 598 before entering the first stage of catalyst.匸. The average temperature of the four-stage catalyst is maintained at around 594 ° C. The reactor and outlet are maintained at atmospheric pressure. As shown in Table 1 below, catalyst deactivation was observed between 854 and 1298 hours of upstream flow time. During this period, the selectivity of ethylbenzene increased slightly due to the decline in ethylbenzene conversion. At 1300 hours, the test unit was closed and a stainless steel container filled with 5.4 grams of ACS grade KOH was placed over aluminum oxide. After the reactor is restarted, a small amount of KOH will continue to vaporize and be used by the reactor. The size of the paper is applicable to China National Standard (CNS) A4 (210X297mm) (please read the precautions on the back and fill in this page)-装 _
'1T 丨線 經濟部中央標準局身工消費合作社印製 A7 B7 五、發明説明（14 ) 一— 餵料流帶入與催化劑接觸。容器的溫度控制得使K0H蒸 汽麼相當於總餵料之約5Ppm(重量比）。在13肺觸小時之 間，發現催化劑活性和選擇性持續改善。然後催化劑活性 保持穩定，與加KOH前相較，轉化率維持於高出約2 3%之 點，苯乙烯選擇率維持於高出约〇.3%之點。於We小時， 添加KOH之乙苯轉化率比如果催化劑以像未引入K〇H前之 相同速率失活，則於相同上物流時間之轉化率高出收44% 。與可比較之乙苯轉化率數據（例如，於854小時）相較下， 添加KOH苯乙烯選擇率比不加K〇H高出〇 4%。 表1 上物流 時間（小時） 854 874 1283 1298 1476 1506 1535 1563 1620 1642 KOH(ppm) 0 0 0 0 5 5 5 5 5 5 總轉化率 (莫利 61.7 61 .7 59.3 59.2 60.9 61.5 61 .4 61.5 61.5 61.6 總選擇率 (莫耳%) 96.6 96.7 96.9 96.7 96.9 97.0 97.0 97.0 97.1 97.1 實例2 將類似實例1所述構成和裝填之第二反應器於上段裝 填32.5克G-84催化劑。於594和^，◦間之平均溫度下、蒸汽 對乙苯比在9和12間、出口壓i4 ?psia、〇和3341小時之間操 作反應器。整個流程中，乙苯餵料的流速保持於與實例1 一樣。如下面表2所示，於彳722和1888小時之間觀察到上段 催化劑之失活’此段溫度維持於597=c上下1°C内。蒸汽對 乙苯比率為12莫耳。於334彳小時，關閉單元，將稍後在不 干擾反應下可裝填K〇(H於其内之過熱器裝設於反應器入口 本紙浪纽 t關家鮮（cn77^^7210x79'7^') ^^1 a^i— 1.^1 —^n n ml ^1. (請先Μ讀背面之注意事項再填寫本頁) •1Τ 丨線 經濟部中央標準局負工消費合作社印製 A7 B7 五、發明説明（15 ) 之上游。俟單元再啓動後，上段催化劑繼續失活，其溫度 推持於622°C上下rc内（表2)。蒸汽對乙苯之比為9，反應 器出口壓為14_7pSja。於3481小時，在不干擾反應下，將7_〇 克ACS級KOH裝填入過熱器中。控制過熱器溫度使少量K〇H 持續汽化並被反應混合液帶入與催化劑接觸。於此等溫度 下KOH之蒸汽壓相當於總餵料之約9ppm(重量比）。於103小 時内’溫度維持於622 °C上下1 °C内，上段中乙苯轉化率很 快地從5_1。/。改善成12·3%，然後於彳76小時内逐漸增加到12 9% ，並維持於此高標準63〇小時。此實例説明立即暴露於餵 料流之催化劑對失活最為敏感且也從本發明方法收到最大 的利益。 表2 上物流 時間（小時）1722 1800 1888 3347 3418 3473 3504 3584 3760 4132 4390 KOH(ppm) 〇 0 0 0 0 0 9 9 9 9 9 上段轉化率9.4 (莫耳%) 8.9 8.3 6,0 56 5.1 6.9 12.3 12.9 12,8 12·? 實例3 將實例2所述之反應器轉動至過熱器中的Κ〇Η耗盡為 止。然後將出口壓和蒸汽對乙苯之比分別調整至6 pSia和8:1 莫耳。上段溫度維持於622°C上下1 °C内。於4731和5022小 時之間觀察到上段催化劑之老化，同時苯乙浠選擇率也衰 退。於5〇22小時，再於過熱器中裝塡另外的190克κ〇Η並控 制過熱器溫度使KOH之蒸汽壓相當於總餵料之約2ppm(重量 比）。於24小時内，上段轉化率從9.2%上升至H.4%，然後 本紙張尺度適用中國國家搮準（CNS ) A4規格（210X297公釐） -------------1T----- (請先聞讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（16) -- 於延長的時間内，穩定於約11·〇% ;上段笨乙缔之選擇率 則從94.8%改善至96.8%，如下面表3所示。 表3 上物流 ---- 時間（小時） 4731 4925 5022 5026 5034 5046 5062 5114 5159 5204 KOH(ppm) 0 0 0 2 2 2 2 — 2 2 —一 2 上段轉化率 11 .0 9.6 9.2 10.1 11.1 11.4 11 .0 11 « (莫耳％) 1 1 · 1 11.1 11 .0 上段選擇率 (莫耳％) 95.0 94.8 94.8 94.5 95.1 96.4 96.7 96.9 96.8 96.7 實例4 於實例3中，四段催化劑之平均溫度維持於上下^ C之内。反應器出口壓為6 psia ’蒸汽對乙苯之比為8.1莫 耳。在裝填第二槽KOH前，於β28和5CM9小時之間，總轉 化率從7〇_4。/。下降至69.3%。總選擇率穩定於96 9。/。。於=22 小時，KOH裝填入過熱器中後’於兩天内總轉化率穩定地 從69·3。/。增加到7〇.4%，然後保持於該高標準以上。承；此期 間，尽乙稀選擇率保持穩定於96.9%，亦即，於高轉化率 下所見之相同選擇率。 (請先聞讀背面之注意事項再填寫本頁) 裝 訂 -線 經濟部中央梂隼局負工消費合作社印製 表4 上物流 時間（小時） 4728 4860 4932 5019 5031 5047 5071 5121 5168 5211 KOH(ppm) 0 0 0 0 2 2 2 2 2 2 總轉化率 (莫耳％) 70.4 70.1 69.7 69.3 69.8 70.2 70.4 70.4 70.5 70.5 總選擇率 (莫耳 96.9 96.9 96.9 96.9 96.8 96.9 96.9 96.9 96.9 97.0 前面實例説明本發明方法對部份失活的催化劑活性之 〜18〜 本纸浪尺度適用中國國家榡率（CNS ) A4規格（210X29*7公着） A 7 ’本卬 3 日 B7 I補充 - ..—— .......—* 五、發明説明（) 恢復和將乙苯成為苯乙晞穩定於高轉化率有效’同時也維 持或改良成為苯乙晞之選擇性。 由於在不偏離與本文相關的本發明之範圍内，上面所 述之裝置和方法可有所改變，因此上面説明内容所含之所 有資料意欲被解釋為説明之用而無限制之意。 圓式中標號之簡單説明 1 餵料流 30 :容器 2 餵料流 32 :餵料 3 反應物流 34 :容器30之内部 4 反應物流 42 :檢測裝置 5 反應物流 44 :電線 6 反應物流 46 :泵或注射裝置 10 導管 50 :第一階反應器 12 物流 52 :再加熱器 14 物流 54 :第二階反應器 20 注射管 62 :檢測裝置 22 水溶液 64 :電線 66 :泵或注射裝置 經濟部中央標準局只工消費合作杜印製 ----------衣-- (請先閱讀背面之注意事項再填寫本頁) 〜1 9〜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）'1T 丨 Printed by the Ministry of Economic Affairs, Central Standards Agency, Workers and Consumers Cooperatives A7 B7 V. Description of the invention (14) I — The feed stream is brought into contact with the catalyst. The temperature of the container is controlled so that the KOH steam is equivalent to about 5 Ppm (weight ratio) of the total feed. Between 13 lung touch hours, catalyst activity and selectivity were found to continue to improve. Then the catalyst activity remained stable. Compared with before the addition of KOH, the conversion rate was maintained at a point higher than about 23%, and the styrene selectivity was maintained at a point higher than about 0.3%. At We hour, the conversion rate of ethylbenzene added with KOH is 44% higher than the conversion rate at the same feed time if the catalyst is deactivated at the same rate as before the introduction of KOH. Compared with comparable ethylbenzene conversion data (for example, at 854 hours), the selectivity of styrene added with KOH was 0.4% higher than that without KOH. Table 1 Logistics time (hours) 854 874 1283 1298 1476 1506 1535 1563 1620 1642 KOH (ppm) 0 0 0 0 5 5 5 5 5 5 Total conversion rate (Morley 61.7 61 .7 59.3 59.2 60.9 61.5 61 .4 61.5 61.5 61.6 Total selectivity (mol%) 96.6 96.7 96.9 96.7 96.9 97.0 97.0 97.0 97.1 97.1 Example 2 A second reactor constructed and packed similar to that described in Example 1 was filled with 32.5 grams of G-84 catalyst in the upper section. In 594 and ^ , At an average temperature of between, the steam to ethylbenzene ratio is between 9 and 12, and the outlet pressure is between i4 psia, 0, and 3341 hours. The flow rate of ethylbenzene feed is maintained at the same rate as in Example 1 throughout the process. The same. As shown in Table 2 below, the deactivation of the upper catalyst was observed between 722 and 1888 hours. The temperature of this segment was maintained within 1 ° C above and below 597 = c. The ratio of steam to ethylbenzene was 12 moles. After 334 hours, the unit was closed, and K could be filled later without disturbing the reaction (the superheater with H in it was installed at the reactor entrance, and the paper was made in Newton and Guan Jiaxian (cn77 ^^ 7210x79'7 ^ ') ^^ 1 a ^ i— 1. ^ 1 — ^ nn ml ^ 1. (Please read the precautions on the back before filling out this page) • 1Τ 丨 Thread A7 B7 printed by the Ministry of Central Standards Bureau Negative Consumer Cooperative V. The upstream of the invention description (15). After the unit restarts, the upper catalyst continues to be deactivated, and its temperature is held within 622 ° C up and down rc (Table 2). The ratio of steam to ethylbenzene was 9, and the reactor outlet pressure was 14_7pSja. At 3481 hours, 7_〇g of ACS grade KOH was filled into the superheater without disturbing the reaction. The superheater temperature was controlled so that a small amount of K〇H Continue to vaporize and be brought into contact with the catalyst by the reaction mixture. At these temperatures, the vapor pressure of KOH is equivalent to about 9 ppm (weight ratio) of the total feed. The temperature is maintained at 622 ° C up and down 1 ° C within 103 hours In the upper section, the conversion rate of ethylbenzene in the upper section quickly improved from 5_1% to 12.3%, then gradually increased to 129% within 76 hours, and maintained at this high standard of 63〇 hours. This example illustrates immediately The catalyst exposed to the feed stream is the most sensitive to deactivation and also receives the greatest benefit from the process of the invention. Table 2 Upper stream time (hours) 1722 1800 1888 3347 3418 3473 3504 3584 3760 4132 4390 KOH (ppm) 〇0 0 0 0 0 9 9 9 9 9 Upper conversion rate 9.4 (mol%) 8.9 8 .3 6,0 56 5.1 6.9 12.3 12.9 12,8 12 ·? Example 3 The reactor described in Example 2 was rotated until the KOH in the superheater was exhausted. Then adjust the outlet pressure and the ratio of steam to ethylbenzene to 6 pSia and 8: 1 moles, respectively. The temperature in the upper section is maintained within 1 ° C up and down 622 ° C. The aging of the upper-stage catalyst was observed between 4731 and 5022 hours, and the selectivity of styrene also declined. At 5022 hours, another 190 g of κ〇Η was charged in the superheater and the superheater temperature was controlled so that the vapor pressure of KOH was equivalent to about 2 ppm (weight ratio) of the total feed. Within 24 hours, the conversion rate in the upper section increased from 9.2% to H.4%, and then this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) ------------- 1T ----- (please read the precautions on the back before filling in this page) A7 B7 V. Description of the invention (16)-stabilized at about 11.10% for an extended period of time; The selection rate improved from 94.8% to 96.8%, as shown in Table 3 below. Table 3 Upper stream-time (hours) 4731 4925 5022 5026 5034 5046 5062 5114 5159 5204 KOH (ppm) 0 0 0 2 2 2 2 — 2 2 — 1 2 Upper conversion rate 11.0 9.6 9.2 10.1 11.1 11.4 11 .0 11 «(mol%) 1 1 · 1 11.1 11 .0 Upper selection rate (mol%) 95.0 94.8 94.8 94.5 95.1 96.4 96.7 96.9 96.8 96.7 Example 4 In Example 3, the average temperature of the four-stage catalyst was maintained Within ^ C. The reactor outlet pressure was 6 psia 'and the steam to ethylbenzene ratio was 8.1 moles. Before filling the second tank of KOH, the total conversion rate was from 70 to 4 between 9 hours of β28 and 5CM. /. It fell to 69.3%. The total selection rate stabilized at 96 9. /. . At = 22 hours, after the KOH was charged into the superheater, the total conversion rate steadily increased from 69 · 3 within two days. /. Increased to 70.4%, and then maintained above this high standard. Commitment; during this period, the selectivity of diluent remained stable at 96.9%, that is, the same selectivity seen at high conversion rates. (Please read the precautions on the back and then fill out this page) Binding-Line Ministry of Economic Affairs, Central Boundary Facility Consumer Cooperative Printed Form 4 Logistics Time (hours) 4728 4860 4932 5019 5031 5047 5071 5121 5168 5211 KOH (ppm ) 0 0 0 0 2 2 2 2 2 2 2 Total conversion (mol%) 70.4 70.1 69.7 69.3 69.8 70.2 70.4 70.4 70.5 70.5 Total selectivity (mol 96.9 96.9 96.9 96.9 96.8 96.9 96.9 96.9 96.9 97.0 The previous examples illustrate the invention Method For the activity of partially deactivated catalysts ~ 18 ~ This paper wave scale is applicable to the Chinese national rate (CNS) A4 specification (210X29 * 7 public) A 7 'Ben I 3rd B7 I supplement-..---- ......— * V. Description of the invention () It is effective to restore and stabilize ethylbenzene into phenethylbenzene at a high conversion rate. It also maintains or improves the selectivity to become phenethylbenzene. Within the scope of the present invention, the above-mentioned devices and methods can be changed, so all the information contained in the above description is intended to be interpreted for illustrative purposes without limitation. A brief description of the reference numbers in the circle is 1 Stream 30: Container 2 feed Stream 32: Feed 3 Reactant stream 34: Inside of container 30 4 Reactant stream 42: Detection device 5 Reactant stream 44: Wire 6 Reactant stream 46: Pump or injection device 10 Catheter 50: First-stage reactor 12 Stream 52: Re Heater 14 Logistics 54: Second-stage reactor 20 Injection tube 62: Detection device 22 Aqueous solution 64: Electric wire 66: Pump or injection device Central Ministry of Economic Affairs, Ministry of Economic Affairs, Central China Bureau of Industrial and Commercial Cooperation, Co., Ltd. Du Printed --------- -Clothing-- (Please read the precautions on the back before filling out this page) ~ 1 9 ~ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm)
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US747494A | 1994-06-30 | 1994-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW294657B true TW294657B (en) | 1997-01-01 |
Family
ID=51565213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW083107590A TW294657B (en) | 1994-06-30 | 1994-08-19 |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TW294657B (en) |
-
1994
- 1994-08-19 TW TW083107590A patent/TW294657B/zh not_active IP Right Cessation
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5695724A (en) | Regeneration and stabilization of dehydrogenation catalyst | |
| EP2373404A1 (en) | Process for increasing the carbon monoxide content of a syngas mixture | |
| JPS5910331B2 (en) | Method for producing chlorinated derivatives of ethylene | |
| CN103648971B (en) | Preparation method suitable for the synthesis gas intermediate for preparing hydrogen | |
| EA007142B1 (en) | Copper-base alloy and its use in carburizing environments | |
| US12570590B2 (en) | Method for manufacturing 2-Chloro-1, 1-difluoroethane (HCFC-142), 1,1,2-trifluoroethane (HFC-143), and (E)-1,2-difluoroethylene (HFO-1132(E)) and/or (Z)-1,2-difluoroethylene (HFO-1132(Z)) | |
| US5739071A (en) | Method and apparatus for regeneratinig and stabilizing dehydrogenation catalysts | |
| JP2001316337A (en) | Method for continuous hydrogenation of aromatic nitro compound using catalyst having low aluminum content | |
| EP3851431A1 (en) | Method for producing 1,1,2-trifluoroethane (hfc-143) | |
| JP5638013B2 (en) | Hydrocarbon dehydrogenation method | |
| JP2018509410A (en) | Process for purification of monochloroacetic acid | |
| TW593232B (en) | Process for the preparation of cyclohexanone oxime | |
| Gómez-Sainero et al. | Hydrodechlorination of carbon tetrachloride in the liquid phase on a Pd/carbon catalyst: kinetic and mechanistic studies | |
| CN111268695A (en) | Reduction of Organonitrile Impurity Levels in HCN from Oxygen Andrussow Process | |
| Willms et al. | Performance of a palladium membrane reactor using an Ni catalyst for fusion fuel impurities processing | |
| JPH06182225A (en) | Catalyst for removing hydrogen from atmosphere containing hydrogen, oxygen and vapor | |
| CA1175210A (en) | Process for the purification of hydrogen chloride obtained by the thermal cracking of 1,2- dichloroethane | |
| WO2006088632A2 (en) | Method and apparatus for addition of aqueous solutions to high temperature processes | |
| NO762638L (en) | PROCEDURES FOR DECOMPOSITION OF HALOGENATED ORGANIC COMPOUNDS. | |
| US3592840A (en) | Production of vinyl acetate | |
| CN106999844A (en) | Oxygen is removed from gas containing hydrocarbon mixture | |
| TW522146B (en) | Preparation of acetic acid and/or methyl acetate in the presence of iridium and platinum | |
| JPS6252103A (en) | Manufacture of hydrogen-containing gas | |
| CN121419955A (en) | Catalytic dehydrogenation methods for cycloalkanes | |
| TW537924B (en) | Process for the production of olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK4A | Expiration of patent term of an invention patent |