TW200831453A - Process for producing propylene - Google Patents

Process for producing propylene Download PDF

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TW200831453A
TW200831453A TW096135332A TW96135332A TW200831453A TW 200831453 A TW200831453 A TW 200831453A TW 096135332 A TW096135332 A TW 096135332A TW 96135332 A TW96135332 A TW 96135332A TW 200831453 A TW200831453 A TW 200831453A
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fluid
carbon number
reactor
hydrocarbon
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TW096135332A
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Chinese (zh)
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TWI405750B (en
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Masashi Yamaguchi
Tohru Setoyama
Kagoto Nakagawa
Fumitaka Utsumi
Shinji Iwade
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Mitsubishi Chem Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Propylene in high yield with the use of a small amount of raw materials is provided, while suppressing a catalyst deterioration, in a process for producing propylene by reacting a raw material of olefin of 4 or more carbon atoms with at least one of methanol and dimethyl ether in the presence of a catalyst.

Description

200831453 九、發明說明： 【發明所屬之技術領域】 本毛明係關於由含有碳數4以上之婦烴、與T醇及二甲 =轉中之至少—者的原料混合物製造㈣的方法。 【先前技術】 乙之方法’習知以來，-般係實施石油腦或 兀、m衣解、減麗輕油之流動接觸分解，近年來則注 ^於=乙稀與2-丁稀作為原料的複分解反應、碳數4以 ^細烴的接觸裂解、再者為以甲醇及二乙基財 上之烯烴與甲醇等之含氧另化：:’=知有以碳數u 烴的方法（專利文獻… 作為原料而製造低級烯 專利文獻1 :美國專利第6888038號 【發明内容】 (發明所欲解決之問題） 習知，已有多數提案作為製造丙稀之 別針對反應與精製進行揭示，但關-成手都刀 =醇等之含氧化合物作為原料的方二有二= ::但並未提案有包括較反應器更下心= 因此，本發明之第一目的在於接 程，其係用於使碳數4以上之烯炉^種新穎且經濟的製 至少-者進行反應以製造7、與甲醇及二曱基鍵中 另一方面’於屬於目前乙烯和丙埽製造法之主流的蒸氣 312XP/發明說明書(補件)/97-01/96135332 200831453 裂解製程中，雖未大幅改變所製造之 但藉由將本發明之製程與塞氣裂解事。丙細的比例， m , 、…札衣解衣耘予以統合，則可明 程大=變乙賴丙料比例。再者，藉由統合此 有效利用彼此製程中所不需要的流懸，故可期 運構出相乘效果更為顯著之有效率的製程。 因=本發明之第二目的在於提供—種新穎且經濟的製 ，、係統合了本製程與蒸氣裂解。 η (解決問題之手段） 3明者等人針對使碳數4以上之稀烴、與甲醇及二甲 ^中至少—者進行反應而得到㈣的反應進行研討“士 果侍到下述之發現。 " :由反應所消耗的稀烴量過多’則芳香族化合物和石壞 專非所需化合物的副產生變得顯著，另一方面，若所消 ΐ烯則丙烯的產率過低。藉由適當地設定溫 二一 i 、分壓、空間速度等之反應條件，而將所消費之 烯烴量控制在某特定範圍内，則可依高選擇率且高產率得 到丙烯。以此種條件進行反應時，由於在反應器出口流^ 中大量含有可成為反應原料之碳數4以上之烯烴，故較\圭 係將此等化合物回收至反應器。 乂土 另一方面，於碳數4以上之烯烴與甲醇及二甲基醚中之 至少一者的反應中，亦生成微量的芳香族化合物和石蠟， 並合有於反應器出口流體中。尤其是於使用含有碳數4以 上之稀烴原料作為石蠟的原料時，反應器出口流體中之石 蠟濃度會增大。由於石蠟類在反應器内幾乎不進行反應， 312XP/發明說明書(補件)/97-01/96135332 200831453 故在與碳數4以上之烯烴一起回收至反應器時，系統内的 石蝶會 >辰細、累積著。因此，較佳係將含有石蝶類之流體 的部分自系統内取出。此情況下，取出的流體較佳係作成 為可有效利用之組成的流體。 另外，若於所回收之碳數4以上之烯烴流體中存在有特 定濃度以上的芳香族化合物，則此等芳香族化合物與碳數 4以上之烯烴的反應、和芳香族化合物與甲醇及二甲基醚 中之至少一者的反應會變得顯著，而不必要地消耗掉所供 給之碳數4以上之烯烴和甲醇及二甲基醚中之至少二 者，故不佳。 再者，在將芳香族化合物供給至反應器時，由於因與上 ?碳數4以上之烯烴的反應中所生成之化合物會使觸媒 =孔堵基而促進觸媒劣化’故較佳係儘可能地將存在於反 應益出口流體中之芳香族化合物從系統内取出，使回收至200831453 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD This invention relates to a method for producing (4) a raw material mixture containing a hydrocarbon having a carbon number of 4 or more and a T-alcohol and a dimethyl group. [Prior Art] The method of B has been implemented as a raw material for the flow contact decomposition of petroleum brain or sputum, m-coating solution, and tartar-light oil. In recent years, it has been used as raw materials for ethylene and 2-butadiene. The metathesis reaction, the carbon number 4 is contact cracking of the fine hydrocarbons, and the oxygenation of the olefins such as methanol and diethyl ether and methanol is further modified:: '= knowing the method of carbon number hydrocarbons ( Patent Document... Production of a lower olefin as a raw material Patent Document 1: US Pat. No. 6,880,038 [Summary of the Invention] (Problems to be Solved by the Invention) Conventionally, many proposals have been made for the reaction and purification as a production of propylene. However, the off-hand-to-hand knife=the oxygen-containing compound such as an alcohol as the raw material has two ==: but it is not proposed to include a lower heart than the reactor. Therefore, the first object of the present invention is to carry out the process. It is used to make a novel and economical system with a carbon number of 4 or more, at least one of which is reacted to produce 7, and the other side of the methanol and the dihydrazyl bond is in the mainstream of the current ethylene and propionate manufacturing method. Vapor 312XP / invention manual (supplement) /97-01/96135332 200831453 In the cracking process, although the process of the present invention is not substantially changed, but the process of the present invention is lysed with the plug gas, the ratio of the fineness, m, , ..., the smock undressing is integrated, and the process can be changed. In addition, by integrating the effective use of the flow suspensions that are not required in the process of each other, it is possible to construct an efficient process with a more significant multiplication effect. It is to provide a novel and economical system, the system combines the process and steam cracking. η (the means to solve the problem) 3 Ming and others are aimed at making the carbon number 4 or more of the rare hydrocarbons, and methanol and dimethyl - The reaction was carried out to obtain the reaction of (4). "The result is that the following results are found: "Excessive amount of dilute hydrocarbons consumed by the reaction", and the secondary compound of the aromatic compound and the stone compound Significantly, on the other hand, if the decene is removed, the yield of propylene is too low. By appropriately setting the reaction conditions of temperature, i, partial pressure, space velocity, etc., the amount of olefin consumed is controlled to some Within a certain range, it can be selected according to high selectivity and high yield. When propylene is obtained under such conditions, since a large amount of olefin having 4 or more carbon atoms which can be used as a reaction raw material is contained in the reactor outlet stream, the compounds are recovered into the reactor. On the one hand, in the reaction of at least one of the olefin having a carbon number of 4 or more and at least one of methanol and dimethyl ether, a trace amount of an aromatic compound and paraffin are also formed, and are combined in the outlet fluid of the reactor, especially in use. When a dilute hydrocarbon raw material having a carbon number of 4 or more is used as a raw material of paraffin, the paraffin concentration in the outlet fluid of the reactor increases. Since the paraffin wax hardly reacts in the reactor, 312XP/Invention Manual (Supplement)/97- 01/96135332 200831453 Therefore, when it is recycled to the reactor together with the olefin having 4 or more carbon atoms, the stone butterfly in the system will be fine and accumulated. Therefore, it is preferred to remove a portion of the fluid containing the stone butterfly from the system. In this case, the fluid to be taken out is preferably made into a fluid which can be effectively utilized. In addition, when an aromatic compound having a specific concentration or more is present in the olefin fluid having a carbon number of 4 or more, the reaction of the aromatic compound with an olefin having 4 or more carbon atoms, and an aromatic compound with methanol and dimethyl The reaction of at least one of the ethers becomes remarkable, and it is unfavorable to unnecessarily consume the supplied olefin having at least 4 carbon atoms and at least two of methanol and dimethyl ether. Further, when the aromatic compound is supplied to the reactor, the catalyst generated by the reaction with the olefin having 4 or more carbon atoms is caused by the catalyst = pore blocking, thereby promoting catalyst deterioration. As far as possible, remove the aromatic compounds present in the reaction benefit outlet fluid from the system and recycle them to

中的芳香族化合物濃度降低。此情況下，取 出的流體較佳係作成為可有效利用之組成的流體。 如此，本發明者等人發現以碳數4以上之烯烴、與 二甲基驗中之至少—者作為原料而製造丙烯之方法 ^種並藉由建射解決此等課㈣製程，而可在 稀。…原料、並抑制觸媒劣化之下，依高產率製造丙 供給至塞氣聲二 藉由將自本製程取出之流體 本f程^= 或將蒸氣裂解製財之流體供給至 、、J了有效利用價值較低的流體，並可實現顯著有 7 200831453 效率的製程。 以下述内容作為其要 本發明係根據此種見解而達成者 旨0 一 [Π-種㈣之製造方法，係將含有碳& 4以上之婦 ^ '、甲醇^一甲基喊中之至少一者的原料，於觸媒存在 下，在反應器中接觸而製造丙稀者；其特徵為， 一將該反應器出口流出氣體(反應器出口氣體）中所含之 2族化合物之至少-部分取出，並且，將該反應器出口 出氣體(反應器出口氣體)中所含之碳冑4以上之烯烴 的至少-部分，於該反應器内再次與觸媒接觸。 上]如⑴之丙稀之製造方法，其中，上述碳數4以上之 烯烴原料係含有碳數4以上之石蠟類。 m如[2]之丙狀製造方法，其中，上述石蟻類係含有 正丁烧及異丁烧中之至少一者。 [4] 如[1]至[3]中任—項之丙烯之製造方法，其中，於 上述供給至反應器之原料中含有 、 [5] 如[1]至[4]中任一項之丙烯之製造方法，其中，於 上述供給至反應器之總原料中所含之芳香族化合物的人 言:量，相對於該總原料所含之碳數4以上之婦烴的合二 量’以莫耳比計為未滿〇. 05。 [6] 如[1]至[5]中任一項之丙烯之製造方法，1中，上 述供給至反應器之碳數4以上之烯烴的量，相對ς該供給 至反應器之甲醇莫耳數與二甲基醚莫耳數之2倍 計’以莫耳比計為〇· 2以上且1 〇以下。 口 312ΧΡ/發明說明書(補件)/97-01/96135332 200831453 ⑺如⑴至[6]中任一項之丙晞之製造方法，苴中，將 ^述供給至反應器之總原料中所含的碳數4以上之稀煙 ”甲知與-曱基㈣合計濃度（基質濃 積％以上且80體積％以下。 ZU體 [8]-種丙稀之製造方法，係將含有碳數4以上之稀 烴、與曱醇二二甲基醚中之至少一者的原料，於觸媒存在 下，在反應器中接觸而製造丙烯者；其特徵為包括含 下步驟（1)、（2)及（3A)之製程； 步驟（1):將碳數4以上之烯烴原料、自步驟（3A)所回 收之烴流體（D)、暨甲醇及二甲基醚中之至少一者，供給 至反應器，依反應ϋ出口之碳數4以上之埽烴之莫耳流量 相對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與上述觸媒接觸，而自反應器出口得到 含有丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體 (反應器出口氣體）之步驟； 步驟（2) ··將來自上述步驟（1)之反應器出口氣體，分離 為富含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（Α)、及富含水之流體之步驟； 步驟（3Α) ··將上述步驟（2)中之流體（Α)之至少一部分的 流體（C)，分離為芳香族化合物濃度較該流體（c)低之流體 (D)、與碳數4之烴濃度較該流體（C)低之流體（E)，將上 述流體（D)回收至反應器，將上述流體（E)自該製程取出之 步驟。 [9 ] 一種丙烯之製造方法，係將含有碳數4以上之烯 3 UXP/發明說明書(補件)/97-01/96135332 9 200831453 烴、與甲醇及二甲基醚中之至少一者的原料，於觸媒存在 下’在反應器中接觸而製造丙烯者；其特徵為包括含有以 下步驟（1)、（2)及（3A)之製程； 步驟(1):將碳數4以上之烯烴原料、自步驟㈤所回 ，收之烴流體⑼、暨甲醇及二甲基峻中之至少一者，供給 至反應器，依反應器出口之碳數4以上之婦煙之莫耳流量 相對於反應器入口之該稀烴之莫耳流量為2〇%以上且未滿 9_反應條件，與域觸雜觸，而自反剌出口得到 i含有丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體 (反應器出口氣體）之步驟； 步驟⑺：將來自上述步驟⑴之反應器出口氣體，分離 為虽含碳數3以下之煙的流體、富含碳數4以上之煙的流 體（A)、及富含水之流體之步驟； 步驟（3A广將上述步驟⑵中之流體⑴之一部分⑻從 該製程取出，將剩餘的流體⑹分離為芳香族化合物濃度 "較該流體⑹低之流體（D)、與碳數4之烴濃度較該流體⑹ 低之抓體(E)，將上述流體⑻回收至反應器 (E)自該製程取出之步驟。 ^ ^ ⑽如[8]或[9]之丙烯之製造方法，其中，上述反應器 包=串聯連接的二個以上的反應部；將上述供給至反應器 之碳數4以上之烯烴原料、甲醇及二甲基醚中之至少一 者、以及所回收之含烴流體（D)中之至少一者，分判為第 1階段反應部與第2階段以後之反應部而進行供給： [11]如[8]至[10]中任一項之丙烯之製造方法，其中， 312XP/發明說明書(補件)/97·〇1/96135332 200831453 將上述流體（B )供給至蒸氣裂解製程，利用作為裂解原料。 [12] 如[11]之丙烤之製造方法’其中’使上述流體（b) 之至少一部分與氫化觸媒接觸後，供給至蒸氣裂解製程。 [13] 如[8]至[12]中任一項之丙烯之製造方法，其中， 上述流體（B)所含之芳香族化合物濃度的合計為未滿5. 〇 體積％。 [14] 如[8]至[13]中任一項之丙烯之製造方法，其中， 將上述流體（E)混合至蒸氣裂解製程之分解汽油館分中。 [15] 如[8]至[14]中任一項之丙烯之製造方法，其中， 上述流體（E)所含之碳數4之烴的合計濃度為未滿5重量 % 〇 [16] 如[8]至[15]中任一項之丙烯之製造方法，其中， 藉由控制上述流體（B)及上述流體（E)之流量，而將上述供 給至反應器之總原料中所含之碳數4以上之烯烴與甲醇 與二曱基醚的合計濃度（基質濃度）控制於2〇體積％以上 且80體積％以下。 ' [17] —種丙烯之製造方法，係將含有碳數4以上之烯 烴、與曱醇及二甲基財之至少—者的混合物，於觸媒存 在下，在反應器中接觸而製造丙烯者；其特徵為，包括含 有以下步驟（1)、（2)及（3B)之製程； 步驟（1) ··將碳數4以上之烯烴原料、自步驟（3B)所回 收之烴流體（I)、暨甲醇及二曱基醚中之至少一者，供給 至反應姦，依反應态出口之碳數4以上之稀烴之莫耳流量 相對於反應器入口之該烯烴之莫耳流量為2〇%以上且未= 312XP/發明說明書(補件)/97-01/96135332 11 200831453 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體（反 應器出口氣體）之步驟； 步驟（2):將來自上述步驟（1)之反應器出口氣體，分離 為富含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（A )、及富含水之流體之步驟； 步驟（3B):將上述步驟（2)中之流體（A)，分離為芳香族 化合物濃度較流體（A)低之流體（G )、與碳數4之煙濃度較 《流體（A)低之流體（F )，將上述流體（g )之至少一部分（I) 回收至反應器，並將剩餘的流體（H)自該製程取出之步驟。 [18]—種丙烯之製造方法，係將含有碳數4以上之烯 烴、與甲醇及二曱基醚中之至少一者的混合物，於觸媒存 在下，在反應器中接觸而製造丙烯者；其特徵為包括含有 以下步驟（1)、（2)及（3B)之製程； 步驟（1):將碳數4以上之烯烴原料、自步驟（3B)所回 收之煙流體（I )、暨曱醇及二甲基_中之至少一者供給至 反應為，依反應裔出口之碳數4以上之稀烴之莫耳流量相 對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體（反 應器出口氣體）之步驟； 步驟（2) ·•將來自上述步驟之反應器出口氣體，分離 為富含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（A )、及富含水之流體之步驟； 312XP/發明說明書(補件)/97-01/96135332 12 200831453 步驟（3B) ··將上述步驟（2)中之流體（幻，分離為芳香族 化合物濃度較流體（A)低之流體（g)、與碳數4之烴濃度較 流體（A)低之流體（F)，將上述流體（f)自該製程取出，並 將上述流體（G)之一部分（I)回收至反應器，並將剩餘的流 • 體（H)自該製程取出之步驟。 [19] 如[17]或[18]之丙稀之製造方法，其中，上述反應 斋包括串聯連接的二個以上的反應部；將上述供給至反應 器之碳數4以上之烯烴原料、甲醇及二甲基醚中之至少一 P者、以及所回收之含烴流體（丨）中之至少一者，分割為第 1階段反應部與第2階段以後之反應部而進行供給。 [20] 如[17]至[19]中任一項之丙烯之製造方法，其中， 將上述流體（H)供給至蒸氣裂解製程，利用作為裂解原料。 [21] 如[20]之丙烯之製造方法，其中，使上述流體（h) 之至少一部分與虱化觸媒接觸後，供給至蒸氣裂解製程。 [22] 如[17]至[21]中任一項之丙烯之製造方法，其中， 上述流體（H)所含之芳香族化合物濃度的合計為未滿5 〇 體積％。 · [23] 如[17]至[22]中任一項之丙烯之製造方法，其中， 將上述流體（F)混合至蒸氣裂解製程之分解汽油餾分中。 [24] 如[17]至[23]中任一項之丙烯之製造方法，其中， 上述流體（F)所含之碳數4之烴的合計濃度為未滿5重量 • %。 里 [25] 如[17]至[24]中任一項之丙烯之製造方法，其中， 藉由控制上述流體（F)及流體（H)之流量，而將上述供給至 312XP/發明說明書(補件)/97-01/96135332 13 200831453 反應器之總原料中所含之碳數4以上之烯烴與曱醇與二 曱基醚的合計濃度（基質濃度）控制於2〇體積％以上且8〇 體積％以下。 [26] 如[8]至[25]中任一項之丙烯之製造方法，其中， 上述步驟（2)係包含藉由冷卻及壓縮步驟而將水分自上述 反應裔出口氣體凝縮去除後，藉由蒸顧，分離為富含碳數 2以下之煙的流體與富含碳數3以上之烴的流體，將上述 富含碳數3以上之烴的流體藉蒸餾分離為富含碳數3之烴 的流體、與富含碳數4以上之烴的流體之步驟。 [27] 如[8]至[25]中任一項之丙烯之製造方法，其中， 上述步驟（2 )係包含藉由冷卻及壓縮步驟而將水分自上述 反應器出口氣體凝縮去除後，藉由蒸餾，分離為富含碳數 3以下之烴的流體與富含碳數4以上之烴的流體，將上述 富含碳數3以下之烴的流體藉蒸餾分離為富含碳數2以下 之烴的流體與富含碳數3之烴的流體之步驟。 [28] 如[8]至[25]中任一項之丙烯之製造方法，其中， 上述步驟（2)係包含藉由冷卻及壓縮步驟而將水分自上述 反應器出口氣體凝縮去除後，藉由蒸餾，分離為富含碳數 2以下之烴的流體及富含碳數3之烴的流體及富含碳數3 以上之烴的流體，將上述富含碳數3以上之烴的流體藉蒸 館分離為富含碳數3之烴的流體與富含碳數4以上之烴的 流體之步驟。 [29] 如[8]至[25]中任一項之丙烯之製造方法，其中， 上述步驟（2)係包含藉由冷卻及壓縮步驟而將水分自上述 312XP/發明說明書(補件)/97-01/96135332 14 200831453 反應器出口氣體凝縮去除後，藉由蒸顧，分離為使富含石户 數3以下之烴的流體與富含碳數4以上之烴的流體，將： 述富含碳數3以下之烴的流體藉蒸顧分離為含有碳數2以 下之經及碳數3之煙的流體、與富含碳數3之烴的流體之 •步驟。 [30] 如⑻至[29]中任-項之㈣之製造方法，其中， 上述碳數4以上之烯烴原料係含有碳數4以上之石蠟類。 [31] 如[3G]之丙烯之製造方法，其中，上述石躐類係含 《 有正丁烷及異丁烷中之至少一者。 [32] 如[8]至[31]中任一項之丙烯之製造方法，其中， 上述供給至反應器之原料中含有丁二烯。 [33] 如[8]至[32]中任一項之丙烯之製造方法，其中， 於上5供給至反應器之總原料中所含之芳香族化合物的 合計量，相對於該總原料所含之碳數4以上之烯烴的合計 量，以莫耳比計為未滿〇. 05。 ^ [34]如[8]至[33]中任一項之丙烯之製造方法，其中， 上述供給至反應器之碳數4以上之烯烴的量，相對於該供 給至反應器之T醇莫耳數與二甲基醚莫耳數之2倍的合 計’以莫耳比計為〇· 2以上且1 〇以下。 [35]如[8]至[34]中任一項之丙烯之製造方法，其中， 上述供給至反應器之碳數4以上之烯烴原料，係含有由蒸 氣4解製程所得之碳數4之烴流體。 一 [36]—種丙烯之製造方法，係將含有碳數4以上之烯 煙、與甲醇及二甲基鍵中之至少一者的混合物，於觸媒存 312XP/發明說明書(補件)/97撕96135332 15 200831453 在下，在反應器中接觸而製造丙烯者；其特徵為，包括含 有以下步驟（1C)、（2C)、（3C)及（4C)之製程； 步驟（1C):將碳數4以上之烯烴原料、自步驟（4C)所回 收之烴流體（Q)、暨甲醇及二曱基醚中之至少一者供給至 • 反應器，依反應器出口之碳數4以上之烯烴之莫耳流量相 對於反應器入口之該烯烴之莫耳流量為20%以上且未滿 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體（反 Γ 應器出口氣體）之步驟； 步驟（2C):將來自上述步驟（1C)之反應器出口氣體冷 卻，分離為氣體流體（L)、富含碳數4以上之烴並含有芳 香族化合物的液流體（M)、及富含水之流體之步驟； 步驟（3C):將上述步驟（2C)中之氣體流體（L)分離為富 含碳數3以下之烴的流體與富含碳數4以上之烴的流體（N) 之步驟； 步驟（4C):將上述流體（N)之至少一部分流體（Q)回收至 t反應器之步驟。 [37]—種丙烯之製造方法，係將含有碳數4以上之烯 烴、與曱醇及二曱基醚中之至少一者的混合物，於觸媒存 在下，在反應器中接觸而製造丙烯者；其特徵為，包括含 • 有以下步驟（1C)、（2C)、（3C)及（4C)之製程； • 步驟（1C):將碳數4以上之烯烴原料、自步驟（4C)所回 收之烴流體（Q)、暨甲醇及二曱基醚中之至少一者供給至 反應器，依反應器出口之碳數4以上之烯烴之莫耳流量相 312XP/發明說明書(補件)/97-01/96135332 16 200831453 對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體（反 ' 應器出口氣體）之步驟； ’步驟（2C):將來自上述步驟（lc)之反應器出口氣體冷 卻，藉壓縮將冷卻後之氣體流體（κ)分離為氣體流體（1〇、 虽含碳數4以上之烴並含有芳香族化合物的液流體（Μ)、 及富含水之流體之步驟； Γ：步驟（3C):將上述步驟（2C)中之氣體流體（L)分離為富 含石反數3以下之烴的流體與富含碳數4以上之烴的流體（ν) 之步驟； 步驟（4C)··將上述流體（N)i一部分（ρ)自該製程取出， 將剩餘的流體（Q)回收至反應器之步驟。 [38] 如[36]或[37]之丙烯之製造方法，其中，藉蒸餾將 上述液流體（M)分離為芳香族化合物濃度較液流體（M)中 低之流體（R)與碳數4之烴濃度較液流體以）低之流體 U (S) 〇 [39] 如[38]之丙烯之製造方法，其中，將上述流體（R) 送回至從上述流體（K)、（L)、（Μ)、（P)及（Q)中選出之任 一或^一以上的流體的流通處。 [40 ]如[36 ]至[39 ]中任一項之丙烯之製造方法，其中， 上述步驟（3C)係包含藉由蒸餾將上述氣體流體（L)分離為 富含碳數2以下之烴的流體與富含碳數3以上之烴的流 體，並進一步藉蒸餾將富含碳數3以上之烴的流體分離^ 312XP/發明說明書(補件)/97-01/96135332 17 200831453 富含碳數3之烴的流體與富含碳數4以上之烴的流體（N) 之步驟。 [41 ]如[36]至[39]中任一項之丙烯之製造方法，其中， ' 上述步驟（3C)係包含藉由蒸餾將上述氣體流體（L)分離為 ’富含碳數3以下之烴的流體與富含碳數4以上之烴的流體 (N) ’並進一步藉蒸餾將富含碳數3以下之烴的流體分離 為富含碳數2以下之烴的流體與富含碳數3之烴的流體之 步驟。 C [42]如[36]至[39]中任一項之丙烯之製造方法，其中， 上述步驟（3C)係包含藉由蒸餾將上述氣體流體（L)分離為 含有碳數2以下之烴與碳數3之烴的流體、及富含碳數3 以上之烴的流體，並進一步藉蒸餾將富含碳數3以上之烴 的流體分離為富含碳數3之烴的流體與富含碳數4以上之 烴的流體（N)之步驟。 [43] 如[36]至[39]中任一項之丙烯之製造方法，其中， 上述步驟（3C)係包含藉由蒸餾將上述氣體流體（L)分離為 /富含碳數3以下之烴的流體與富含碳數4以上之烴的流體 (N)，並進一步藉蒸餾將富含碳數3以下之烴的流體分離 為含有碳數2以下之烴與碳數3之烴的流體、及富含碳數 3之烴的流體之步驟。 [44] 如[36]至[43]中任一項之丙浠之製造方法，其中， • 上述反應為包括串聯連接的二個以上的反應部；將上述供 給至反應器之碳數4以上之烯烴原料、曱醇及二甲基趟中 之至少一者、暨所回收之含烴流體中之至少一者，分割為 312XP/發明說明書(補件)/97-01/96135332 18 200831453 第1階段反應部與第2階段以後之反應部而進行供給。 [45]如[36]至[44]中任一項之丙稀之製造方法，其中， 上述碳數4以上之烯烴原料係含有碳數4以上之石蠟類。 ' [46]如[45]之丙稀之製造方法，其中，上述石蠟類係含 * 有正丁烧及異丁烧中之至少一者。 [47] 如[36]至[46]中任一項之丙烯之製造方法，其中， 於上述供給至反應器中之原料中含有丁二稀。 [48] 如[36]至[47]中任一項之丙烯之製造方法，其中， ί於上述供給至反應器之總原料中所含之芳香族化合物的 合計量，相對於該總原料所含之碳數4以上之烯烴的合計 里’以莫耳比汁為未滿0.05。 [49] 如[36]至[48]中任一項之丙烯之製造方法，其中， 將上述流體（Μ)及上述流體（ρ)中之至少一者供給至蒸氣 裂解製程，利用作為裂解原料。 μ乳 [50] 如[49]之丙烯之製造方法，其中，使上述流體（μThe concentration of aromatic compounds in the mixture is lowered. In this case, the fluid to be taken out is preferably a fluid which is a composition which can be effectively utilized. As described above, the inventors of the present invention have found that a method for producing propylene by using at least one of a olefin having a carbon number of 4 or more and at least one of a dimethyl group as a raw material can be solved by the formation of the fourth (4) process. dilute. ...the raw material, and inhibiting the deterioration of the catalyst, the supply of C to the gas is produced according to the high yield. By supplying the fluid taken out from the process, or the fluid for vapor cracking, the J is supplied. Efficient use of lower value fluids and a significant process with 7 200831453 efficiency. The present invention is based on the above-mentioned findings. The method for producing a method according to the above-mentioned findings is to produce at least a woman having a carbon & a raw material, in the presence of a catalyst, is contacted in a reactor to produce a propylene; characterized in that at least one of the Group 2 compounds contained in the gas (reactor outlet gas) exiting the reactor outlet is - Partially withdrawn, and at least a portion of the olefins above the carbon enthalpy 4 contained in the gas (reactor outlet gas) exiting the reactor is again contacted with the catalyst in the reactor. The method for producing propylene according to the above aspect, wherein the olefin raw material having 4 or more carbon atoms contains paraffin having 4 or more carbon atoms. The method for producing a propylene according to [2], wherein the stone ant type contains at least one of n-butyl sinter and isobutyl sinter. [4] The method for producing propylene according to any one of [1] to [3], wherein the raw material supplied to the reactor contains [5] as in any one of [1] to [4]. A method for producing propylene, wherein the amount of the aromatic compound contained in the total raw material supplied to the reactor is equal to or greater than the total amount of the hydrocarbon having 4 or more carbon atoms contained in the total raw material Moerby counts as less than 〇. 05. [6] The method for producing propylene according to any one of [1] to [5], wherein the amount of the olefin having a carbon number of 4 or more supplied to the reactor is relative to the amount of methanol supplied to the reactor. The number and the number of moles of dimethyl ether are 2 times, and the molar ratio is 〇·2 or more and 1 〇 or less. 312 ΧΡ / 发明 发明 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The total concentration of the rare carbon of the carbon number of 4 or more, "Knowledge and - thiol (4) (the concentration of the matrix is more than 80% by volume). The method for producing ZU body [8] - propylene is more than 4 carbon atoms. a raw material of at least one of a dilute hydrocarbon and a sterol didimethyl ether, which is contacted in a reactor to produce propylene in the presence of a catalyst; characterized by comprising the following steps (1), (2) And (3A) the process; the step (1): supplying at least one of the olefin raw material having a carbon number of 4 or more, the hydrocarbon fluid (D) recovered from the step (3A), and methanol and dimethyl ether to The reactor is in contact with the above catalyst according to the reaction condition of the mole flow rate of the hydrocarbon having a carbon number of 4 or more according to the reaction enthalpy of the reaction with respect to the molar flow rate of the olefin of the reactor inlet of 2% or more and less than 90%. And a gas containing propylene and other olefins, paraffins, aromatic compounds and water from the outlet of the reactor (reactor outlet gas) Step; (2) · separating the reactor outlet gas from the above step (1) into a fluid rich in carbon atoms of 3 or less, a fluid rich in carbon 4 or more, And a step of enriching the water; step (3Α) · separating at least a portion of the fluid (C) of the fluid (Α) in the above step (2) into a lower concentration of the aromatic compound than the fluid (c) The fluid (D), the fluid (E) having a lower hydrocarbon concentration than the fluid (C), and the fluid (D) are recovered into the reactor, and the fluid (E) is taken out from the process. 9] A method for producing propylene, which comprises a raw material containing at least one of a hydrocarbon having a carbon number of 4 or more, a U 3 UXP/invention specification (supplement)/97-01/96135332 9 200831453, and methanol and dimethyl ether. a process for producing propylene by contacting in a reactor in the presence of a catalyst; characterized by comprising a process comprising the following steps (1), (2) and (3A); and step (1): olefin having a carbon number of 4 or more The raw material, returned from the step (5), and at least one of the hydrocarbon fluid (9), the methanol and the dimethyl group are supplied to the reactor. The molar flow rate of the female cigarette having a carbon number of 4 or more at the outlet of the reactor is 2% or more with respect to the molar flow of the rare hydrocarbon at the inlet of the reactor, and is less than 9_reaction conditions, and is counter-contact with the domain, and reflexive The 剌 outlet obtains a step of i containing a gas of propylene and other olefins, paraffin, aromatic compound and water (reactor outlet gas); step (7): separating the outlet gas of the reactor from the above step (1) into a carbon number of 3 a fluid of the following smoke, a fluid (A) rich in carbon 4 or more, and a water-rich fluid; step (3A widely extracting a portion (8) of the fluid (1) in the above step (2) from the process, The remaining fluid (6) is separated into a concentration of the aromatic compound " a fluid (D) lower than the fluid (6), and a slurry (E) having a lower hydrocarbon concentration than the fluid (6), and the fluid (8) is recovered to the reactor. (E) The step of taking out from the process. (10) The method for producing propylene according to [8] or [9] wherein the reactor package includes two or more reaction units connected in series; and the olefin raw material or methanol having a carbon number of 4 or more supplied to the reactor And at least one of the dimethyl ether and at least one of the recovered hydrocarbon-containing fluids (D) are supplied as a first-stage reaction unit and a reaction unit after the second stage: [11] The method for producing propylene according to any one of [8] to [10] wherein, the 312XP/invention specification (supplement)/97·〇1/96135332 200831453 supplies the fluid (B) to a steam cracking process, and uses Crack the raw material. [12] The method for producing propylene according to [11], wherein at least a part of the fluid (b) is brought into contact with a hydrogenation catalyst, and then supplied to a vapor cracking process. [A] The method for producing propylene according to any one of [8] to [12] wherein the total concentration of the aromatic compound contained in the fluid (B) is less than 5% by volume. [14] The method for producing propylene according to any one of [8] to [13] wherein the fluid (E) is mixed into a decomposition gasoline column of the steam cracking process. [15] The method for producing propylene according to any one of [8] to [14] wherein the total concentration of hydrocarbons having a carbon number of 4 contained in the fluid (E) is less than 5% by weight 〇 [16] The method for producing propylene according to any one of [8], wherein the flow rate of the fluid (B) and the fluid (E) is controlled to be supplied to the total raw material of the reactor. The total concentration (matrix concentration) of the olefin having a carbon number of 4 or more and methanol and dimethyl ether is controlled to 2% by volume or more and 80% by volume or less. [17] A method for producing propylene, which comprises a mixture of an olefin having 4 or more carbon atoms and at least a sterol and a dimethyl group, and is contacted in a reactor to produce propylene in the presence of a catalyst. And characterized in that it comprises a process comprising the following steps (1), (2) and (3B); Step (1) · A hydrocarbon raw material having a carbon number of 4 or more and a hydrocarbon fluid recovered from the step (3B) I), at least one of methanol and dimethyl ether, is supplied to the reaction, and the molar flow of the hydrocarbon having a carbon number of 4 or more depending on the reaction state is relative to the molar flow of the olefin at the inlet of the reactor. 2% or more and not = 312XP / invention manual (supplement) / 97-01/96135332 11 200831453 90% of the reaction conditions, contact with the catalyst, and from the reactor outlet to obtain propylene and other olefins, paraffin, aromatic Step of the gas of the group compound and water (reactor outlet gas); Step (2): separating the outlet gas of the reactor from the above step (1) into a fluid rich in carbon atoms of 3 or less, carbon-rich a step of a fluid (A) of a hydrocarbon of 4 or more, and a fluid rich in water; 3B): separating the fluid (A) in the above step (2) into a fluid having a lower aromatic compound concentration than the fluid (A) and a fluid having a lower carbon concentration than the fluid (A) (F), a step of recovering at least a portion (I) of the above fluid (g) to the reactor and taking out the remaining fluid (H) from the process. [18] A method for producing propylene, which comprises contacting a mixture of at least one of an olefin having 4 or more carbon atoms and methanol and a dimethyl ether in a reactor in the presence of a catalyst to produce propylene. And characterized in that it comprises a process comprising the following steps (1), (2) and (3B); Step (1): a olefin raw material having a carbon number of 4 or more, a smoke fluid (I) recovered from the step (3B), At least one of cuminol and dimethyl group is supplied to the reaction, wherein the molar flow of the hydrocarbon having a carbon number of 4 or more according to the reactant outlet is 2% by mole relative to the molar flow of the olefin at the inlet of the reactor. Above and below 90% of the reaction conditions, in contact with the catalyst, a step of obtaining a gas containing propylene and other olefins, paraffins, aromatic compounds and water (reactor outlet gas) from the reactor outlet; step (2) • The step of separating the reactor outlet gas from the above steps into a fluid rich in carbon atoms of 3 or less, a fluid (A) rich in carbon 4 or more, and a fluid rich in water; 312XP/ Invention specification (supplement) /97-01/96135332 12 200831453 Step (3B) · The fluid in the above step (2) (phantom, separated into a fluid having a lower concentration of the aromatic compound than the fluid (A), and a fluid having a lower hydrocarbon concentration than the fluid (A) (F), The above fluid (f) is taken out from the process, and a part (I) of the above fluid (G) is recovered to the reactor, and the remaining fluid (H) is taken out from the process. [19] The method for producing acryl according to [18], wherein the reaction mixture comprises two or more reaction units connected in series; and the olefin raw material, methanol and dimethyl ether having a carbon number of 4 or more supplied to the reactor At least one of the P and the recovered hydrocarbon-containing fluid (丨) are divided into a first-stage reaction unit and a reaction unit after the second stage, and are supplied. [20] [17] to [ The method for producing propylene according to any one of the preceding claims, wherein the fluid (H) is supplied to a steam cracking process and used as a cracking raw material. [21] The method for producing propylene according to [20], wherein the fluid is h) at least a portion of which is contacted with a deuterated catalyst and supplied to a vapor cracking process. [22] As [17] [21] The method for producing propylene according to any one of the preceding claims, wherein the total concentration of the aromatic compounds contained in the fluid (H) is less than 5% by volume. [23] as in [17] to [22] And a method for producing propylene according to any one of [17] to [23], wherein the propylene is produced by the method of the present invention, wherein the propylene is produced by the method of any one of [17] to [23], wherein The method for producing a propylene having a carbon number of 4 in the fluid (F) is less than 5% by weight. The method for producing propylene according to any one of [17] to [24], wherein The above-mentioned fluid (F) and the flow rate of the fluid (H) are controlled to supply the above-mentioned carbon to the 312XP/invention specification (supplement)/97-01/96135332 13 200831453. The total concentration (base concentration) of the olefin, decyl alcohol and dimethyl ether is controlled to be 2% by volume or more and 8% by volume or less. [26] The method for producing propylene according to any one of [8] to [25] wherein the step (2) comprises condensing and removing water from the reaction source outlet gas by a cooling and compression step, and then borrowing Divided into a fluid rich in carbon number 2 or less and a fluid rich in carbon 3 or more by steaming, and the above-mentioned fluid having a carbon number of 3 or more is separated into a carbon-rich number 3 by distillation. A step of a fluid of a hydrocarbon and a fluid rich in hydrocarbons having a carbon number of 4 or more. [27] The method for producing propylene according to any one of [8] to [25] wherein the step (2) comprises condensing and removing water from the outlet gas of the reactor by a cooling and compression step, Dividing into a fluid rich in hydrocarbons having a carbon number of 3 or less and a fluid having a hydrocarbon having a carbon number of 4 or more by distillation, and separating the fluid having a hydrocarbon having a carbon number of 3 or less by distillation into a carbon number of 2 or less A step of a hydrocarbon fluid and a fluid having a carbon number 3 hydrocarbon. [28] The method for producing propylene according to any one of [8] to [25] wherein, in the step (2), the water is condensed and removed from the outlet gas of the reactor by a cooling and compression step, Dividing into a fluid rich in carbon atoms of 2 or less and a fluid rich in carbon number 3 and a fluid rich in carbons of 3 or more by distillation, and borrowing the fluid having a hydrocarbon having 3 or more carbon atoms The steaming plant is separated into a fluid having a carbon number 3-rich hydrocarbon and a fluid rich in carbon 4 or more hydrocarbons. [29] The method for producing propylene according to any one of [8] to [25] wherein the step (2) comprises the step of cooling and compressing the water from the above-mentioned 312XP/invention specification (supplement)/ 97-01/96135332 14 200831453 After the reactor outlet gas is condensed and removed, it is separated into a fluid rich in hydrocarbons having a rock number of 3 or less and a hydrocarbon rich in carbon 4 or more by steaming. A step of separating a fluid containing a hydrocarbon having a carbon number of 3 or less into a fluid containing a carbon number of 2 or less and a carbon of 3 carbon atoms, and a fluid having a carbon number of 3 carbon. The production method of the above-mentioned item (4), wherein the olefin raw material having 4 or more carbon atoms contains a paraffin wax having 4 or more carbon atoms. [31] The method for producing propylene according to [3G], wherein the sarcophagus contains "at least one of n-butane and isobutane." [32] The method for producing propylene according to any one of [8] to [31] wherein the raw material supplied to the reactor contains butadiene. [33] The method for producing propylene according to any one of [8] to [32] wherein the total amount of the aromatic compound contained in the total raw material supplied to the reactor in the upper 5 is relative to the total raw material The total amount of olefins having a carbon number of 4 or more is not more than 莫. 05. The method for producing propylene according to any one of [8] to [33] wherein the amount of the olefin having a carbon number of 4 or more supplied to the reactor is relative to the amount of the alcohol supplied to the reactor. The total number of ears and twice the number of dimethyl ether moles is 〇·2 or more and 1 〇 or less in terms of molar ratio. The method for producing propylene according to any one of [8] to [34] wherein the olefin raw material having a carbon number of 4 or more supplied to the reactor contains a carbon number of 4 obtained by a steam 4 decomposition process. Hydrocarbon fluid. [36] A method for producing propylene, which comprises mixing a mixture of at least one of carbonaceous carbon having a carbon number of 4 or more with methanol and a dimethyl bond in a catalyst storage 312XP/invention specification (supplement)/ 97 tearing 9613532 15 200831453 below, in the reactor contact to produce propylene; characterized by including the following steps (1C), (2C), (3C) and (4C) process; step (1C): carbon The olefin raw material of 4 or more, the hydrocarbon fluid (Q) recovered from the step (4C), the methanol and the dimethyl ether are supplied to the reactor, and the olefin having 4 or more carbon atoms at the outlet of the reactor The molar flow rate is 20% or more and less than 90% of the reaction conditions of the olefin at the inlet of the reactor, and is contacted with the catalyst, and the propylene and other olefins, paraffins, and aromatics are obtained from the outlet of the reactor. a step of a gas of a compound and water (reverse gas of the reactor); a step (2C): cooling the outlet gas of the reactor from the above step (1C), separating into a gas fluid (L), having a carbon number of 4 or more a fluid (M) and a rich hydrocarbon containing an aromatic compound Step of water-containing fluid; Step (3C): separating the gas fluid (L) in the above step (2C) into a fluid rich in hydrocarbons having a carbon number of 3 or less and a fluid rich in hydrocarbons having a carbon number of 4 or more (N) Step; Step (4C): a step of recovering at least a part of the fluid (Q) of the above fluid (N) to the t reactor. [37] A method for producing propylene, which comprises contacting a mixture of at least one of an olefin having 4 or more carbon atoms and a decyl alcohol and a decyl ether in a reactor to produce propylene. The method includes: a process comprising the following steps (1C), (2C), (3C), and (4C); • a step (1C): using an olefin starting material having a carbon number of 4 or more, from the step (4C) At least one of the recovered hydrocarbon fluid (Q), cum methanol and dimethyl ether is supplied to the reactor, and the molar flow phase of the olefin having a carbon number of 4 or more according to the outlet of the reactor is 312XP/invention specification (supplement) /97-01/96135332 16 200831453 The reaction conditions for the olefin molar flow rate of the olefin of the reactor inlet being 2% or more and less than 90% are contacted with the catalyst, and propylene and other olefins are obtained from the outlet of the reactor. a step of paraffin, aromatic compound and water gas (reverse gas outlet gas); 'step (2C): cooling the outlet gas of the reactor from the above step (lc), and compressing the cooled gas fluid ( κ) is separated into a gaseous fluid (1〇, although containing more than 4 carbon atoms and a liquid fluid (Μ) having an aromatic compound, and a step of enriching the water; Γ: step (3C): separating the gas fluid (L) in the above step (2C) into a gas-rich number of 3 or less a step of a fluid of a hydrocarbon and a fluid (ν) rich in hydrocarbons having a carbon number of 4 or more; Step (4C) · taking a part (ρ) of the fluid (N) i out of the process, and recovering the remaining fluid (Q) [38] The method for producing propylene according to [36] or [37], wherein the liquid fluid (M) is separated by distillation into a fluid having a lower aromatic compound concentration than the liquid fluid (M) (R) a fluid having a carbon number of 4 and a lower concentration of a fluid than the liquid fluid U (S) 〇 [39] The method for producing propylene according to [38], wherein the fluid (R) is returned to the fluid The circulation of any one or more of the selected ones of (K), (L), (Μ), (P), and (Q). [40] The method for producing propylene according to any one of [36] to [39] wherein the step (3C) comprises separating the gas fluid (L) into a hydrocarbon having a carbon number of 2 or less by distillation. a fluid and a fluid rich in hydrocarbons having a carbon number of 3 or more, and further separating a fluid rich in hydrocarbons having a carbon number of 3 or more by distillation. 312XP/Invention Manual (Supplement)/97-01/96135332 17 200831453 Carbon-rich A step of fluid of a number 3 hydrocarbon and a fluid (N) rich in hydrocarbons having a carbon number of 4 or more. [41] The method for producing propylene according to any one of [36] to [39] wherein, the above step (3C) comprises separating the gas fluid (L) into a carbon-rich number of 3 or less by distillation. a fluid of a hydrocarbon and a fluid (N) rich in hydrocarbons having a carbon number of 4 or more and further separating a fluid having a hydrocarbon having a carbon number of 3 or less into a fluid having a carbon number of 2 or less and a carbon rich by distillation The step of the fluid of the number 3 hydrocarbon. The method for producing propylene according to any one of [36] to [39] wherein the step (3C) comprises separating the gas fluid (L) into a hydrocarbon having a carbon number of 2 or less by distillation. a fluid having a carbon number of 3 and a fluid having a carbon number of 3 or more, and further separating a fluid having a carbon number of 3 or more by a distillation into a fluid rich in a carbon number 3 hydrocarbon and enriched A step of fluid (N) of a hydrocarbon having a carbon number of 4 or more. [43] The method for producing propylene according to any one of [36] to [39] wherein the step (3C) comprises separating the gas fluid (L) into/behaving a carbon number of 3 or less by distillation. a fluid of a hydrocarbon and a fluid (N) rich in hydrocarbons having a carbon number of 4 or more, and further separating a fluid having a hydrocarbon having a carbon number of 3 or less into a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms by distillation And a step of fluid rich in carbon number 3 hydrocarbons. [44] The method for producing a hydrazine according to any one of [36] to [43] wherein: the reaction is two or more reaction units connected in series; and the carbon number supplied to the reactor is 4 or more At least one of the olefinic raw material, decyl alcohol and dimethylhydrazine, and at least one of the recovered hydrocarbon-containing fluids is divided into 312XP/invention specification (supplement)/97-01/96135332 18 200831453 1 The stage reaction unit is supplied to the reaction unit after the second stage. [45] The method for producing propylene according to any one of [36] to [44] wherein the olefin raw material having 4 or more carbon atoms contains a paraffin wax having a carbon number of 4 or more. [46] The method for producing a propylene according to [45], wherein the paraffin wax contains at least one of n-butylene and isobutylidene. [47] The method for producing propylene according to any one of [36] to [46] wherein the raw material supplied to the reactor contains dibutyl slag. [48] The method for producing propylene according to any one of [36] to [47] wherein the total amount of the aromatic compound contained in the total raw material supplied to the reactor is relative to the total raw material The total amount of olefins having a carbon number of 4 or more is less than 0.05 in the molar ratio of the molar ratio. [49] The method for producing propylene according to any one of [36] to [48] wherein at least one of the fluid (Μ) and the fluid (ρ) is supplied to a steam cracking process, and is used as a cracking raw material. .乳乳 [50] The method for producing propylene according to [49], wherein the above fluid (μ

及上述流體⑺中之至少—者的至少—部分與氫化觸媒接 觸後，供給至蒸氣裂解製程。 [51] 如[36]至[50]中任一項之丙烯之製造方法，其中， 上述流體（Μ)及上述流體（ρ)中之至少一者所含之芳夭族 化合物濃度的合計為未滿5 · 〇體積％。 、 [52] 如[36]至[51]中任一項之丙烯之製造方法，其中， 將上述流體（Μ)混合至蒸氣裂解製程之分解汽油鶴分中。 [53] 如[36]至[52]中任一項之丙烯之製造方法，其中， 上述流體（Μ)所含之碳數4之烴的合計濃度為未滿f重量 312XP/發明說明書(補件)/97-01/96135332 19 200831453 % 0 [54] 如[36]至[53]中任一項之丙烯之製造方法，其中， 藉由控制上述流體（M)及上述流體（p)之流量，而將上述供 給至反應裔之總原料中所含之碳數4以上之烯烴與曱醇 •與二曱基醚的合計濃度（基質濃度）控制於20體積％以上 且80體積％以下。 [55] 如[38]至[54]中任一項之丙烯之製造方法，其中， 將上述流體（R)供給至蒸氣裂解製程，利用作為裂解原料。 Γ; [56]如[55]之丙烯之製造方法，其中，使上述流體（R) 之至少一部分與氫化觸媒接觸後，供給至蒸氣裂解製程。 [57] 如[38]至[56]中任一項之丙烯之製造方法，其中， 上述流體（R)中所含之芳香族化合物濃度的合計為未滿 5. 0體積％。 [58] 如[38]至[57]中任一項之丙烯之製造方法，其中， 將上述流體（S)混合至蒸氣裂解製程之分解汽油餾分中。 [59] 如[38]至[58]中任一項之丙烯之製造方法，其中， 上述流體（S)所含之碳數4之烴的合計濃度為未滿5重量 % 〇 [60] 如[38]至[59]中任一項之丙烯之製造方法，其中， 藉由控制上述流體（P)、流體（R)及流體（s)之流量，而將 •上述供給至反應器之總原料中所含之碳數4以上之烯烴 與甲醇與一甲基醚的合計濃度（基質濃度）控制於2〇體積 %以上且80體積％以下。 [61] 如[38]至[60]中任一項之丙烯之製造方法，其中， 312XP/發明說明書(補件)/97-01/96135332 20 200831453 將上述流體（R)送回至從上述流體（Κ)、（L)、（N)、（P)及 (Q)中選出之任-或二以上的流體的流通處；藉由控制上 t㈣°°之送回處及其流量，而將上述供給至反應器之 ^原射所含之碳數4以上之烯烴與甲醇與二曱基_的 合計濃度（基質濃度）控制於20體積％以上且80體積％以 下。 [叫如[36]至[61]中任一項之丙烯之製造方法，其中， 上述供給至反應器之碳數4以上之烯烴的量，相對於該供 給至反應益之曱醇莫耳數與二甲基醚莫耳數之2倍的合 计，以莫耳比計為〇· 2以上且10以下。 [叫如[36]至[62]中任一項之丙稀之製造方法，其令， 士述供給至反應器之碳數4以上之烯烴原料，係含有由蒸 氣裂解製程所得之碳數4之烴流體。 (發明效果） 根據本發明’係-種在觸媒存在下，將含有碳數4以上 =烯煙、與甲醇及二甲基_中之至少—者的原料反應而製 這丙烯的方法，其可向度地利用原料，並在抑制觸媒劣化 之下，以高產率製造丙烯。 ” 又’可將本發明之方法與蒸氣裂解製程統合 的製程。 * 【實施方式】 以下，具體說明用於實施本發明之代表性態樣，但本 明在不超過其要旨之下，並不限定於以下態樣。 本發明之丙烯之製造方法，係將含有碳數4以上之烯 312XP/發明說明書(補件)/97-01/96135332 21 200831453 L與甲知及二甲基峻中之至 下，在反應器令接觸而製：“觸媒存在 器出口流出氣體中所含之芳香特徵為，將該反應 出，同時將該反應器二::出香二，至少-部分取 婦烴的至少-部分於兮反庫出二體中所含之碳數4以上之 作為更具體之第」：第：二再：與觸媒接觸。 1個步驟⑴、(2)、(3^ 第二態樣，係如上述γ t ~ # 又作為 '及⑽者，但在解:本 ⑹ 二:4個步驟的前後亦可存在二;驟4 於各步驟之間亦可存在其他步驟。 ^ ^ ^ ^7] J ^ 0 ^ ^ ^ Λ 50 ^ 佳…以上。At least a portion of at least one of the fluids (7) is contacted with a hydrogenation catalyst and supplied to a vapor cracking process. [51] The method for producing propylene according to any one of [36] to [50] wherein the total concentration of the lanthanum compound contained in at least one of the fluid (Μ) and the fluid (ρ) is Less than 5 · 〇 volume %. [52] The method for producing propylene according to any one of [36] to [51] wherein the fluid (Μ) is mixed into a pyrolysis crane of a steam cracking process. [53] The method for producing propylene according to any one of [36] to [52] wherein the total concentration of the hydrocarbon having a carbon number of 4 contained in the fluid (Μ) is less than the weight of the weight 312XP/invention specification (complement) [54] The method for producing propylene according to any one of [36] to [53] wherein, by controlling the fluid (M) and the fluid (p) In the flow rate, the total concentration (base concentration) of the olefin and the decyl alcohol and the dimethyl ether contained in the total amount of the above-mentioned raw materials supplied to the reactants is controlled to be 20% by volume or more and 80% by volume or less. [55] The method for producing propylene according to any one of [38] to [54] wherein the fluid (R) is supplied to a steam cracking process and used as a cracking raw material. [56] The method for producing propylene according to [55], wherein at least a part of the fluid (R) is brought into contact with a hydrogenation catalyst, and then supplied to a vapor cracking process. [57] The method for producing propylene according to any one of [38] to [56] wherein the total concentration of the aromatic compounds contained in the fluid (R) is less than 5% by volume. [58] The method for producing propylene according to any one of [38] to [57] wherein the fluid (S) is mixed into a decomposition gasoline fraction of a steam cracking process. [59] The method for producing propylene according to any one of [38] to [58] wherein the total concentration of the hydrocarbon having a carbon number of 4 contained in the fluid (S) is less than 5% by weight 60 [60] The method for producing propylene according to any one of [58], wherein the total of the above-mentioned supply to the reactor is controlled by controlling the flow rates of the fluid (P), the fluid (R), and the fluid (s). The total concentration (base concentration) of the olefin having 4 or more carbon atoms and the methanol and monomethyl ether contained in the raw material is controlled to be 2% by volume or more and 80% by volume or less. [61] The method for producing propylene according to any one of [38] to [60] wherein, the 312XP/invention specification (supplement)/97-01/96135332 20 200831453 returns the above fluid (R) to the above The flow of any one or more of the fluids selected from the fluids (Κ), (L), (N), (P), and (Q); by controlling the return of the t(four) °° and its flow rate, The total concentration (matrix concentration) of the olefin having a carbon number of 4 or more and the methanol and the dimercapto group contained in the raw material supplied to the reactor is controlled to be 20% by volume or more and 80% by volume or less. The method for producing propylene according to any one of [36] to [61] wherein the amount of the olefin having 4 or more carbon atoms supplied to the reactor is relative to the molar amount of sterol supplied to the reaction The total of twice the molar amount of dimethyl ether is 〇·2 or more and 10 or less in terms of molar ratio. [The manufacturing method of the propylene according to any one of [36] to [62], wherein the olefin raw material having a carbon number of 4 or more supplied to the reactor contains the carbon number obtained by the steam cracking process 4 Hydrocarbon fluid. (Effect of the Invention) According to the present invention, a method of producing a propylene by reacting a raw material containing a carbon number of 4 or more = olefinic tobacco and at least one of methanol and dimethyl groups in the presence of a catalyst The raw material can be used to a large extent, and propylene can be produced in a high yield under the inhibition of deterioration of the catalyst. And a process for integrating the method of the present invention with a vapor cracking process. * [Embodiment] Hereinafter, a representative aspect for carrying out the present invention will be specifically described, but the present invention does not exceed the gist of the present invention. The method for producing propylene according to the present invention is to contain a olefin 312XP having a carbon number of 4 or more/inventive specification (supplement)/97-01/96135332 21 200831453 L and a known and dimethyl group. At the bottom, in the reactor, the contact is made: "The aromatic characteristic contained in the gas flowing out of the catalyst present outlet is that the reaction is taken out, and at the same time, the reactor two:: aroma 2, at least - part of the female hydrocarbon At least - part of the more than the carbon number contained in the 二 库 库 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二One step (1), (2), (3^ second aspect, such as the above γ t ~ # again as ' and (10), but in the solution: this (6) two: four steps before or after the existence of two; 4 There may be other steps between the steps. ^ ^ ^ ^7] J ^ 0 ^ ^ ^ Λ 50 ^ Good... above.

C 上、更佳9°莫他上、再更佳心 [觸媒] 首先，針對本發明所使用之觸媒進行說明。 (：B (¾為月之反應所用的觸媒，若為具有布忍司特酸位 i:rr:dsite)之固趙狀者’則無特別限定’可:吏 算：二入如南嶺土等之黏土礦物；將硫酸、磷酸 以二 土礦物等之载體上者;酸性型離子 乂換樹月曰，彿石類；磷酸鋁類；Α卜MCM41等之中孔性 312XP/發明說明書(補件)/97·〇ι/96〗35332 200831453 (mesoporous)二氧化石夕氧化铭等之固體酸觸媒。 此等固體酸觸媒中，較佳係具有分子篩效果者，又，較 佳係酸強度不太高者。 上述固體酸觸媒中，作為具有分子篩效果的沸石類和磷 酸铭類之構造，若以 International Zeolite Association(IZA)所規定的編碼表示，則可舉例如ΑΕΙ、 ΑΕΤ、AEL、AFI、AF0、AFS、AST、ΑΤΝ、ΒΕΑ、CAN、CHA、 EMT、ERI、EUO、FAU、FER、LEV、LTL、MAZ、MEL、MFI、 Γ' MOR 、 MTT 、 MTW 、 MWW 、 OFF 、 PAU 、 RHO 、 STT 、 TON 等。其 中，較佳係觸媒之骨架密度為18. OT/nm3以下的觸媒，作 為此種者，較佳可舉例如MFI、MEL、M0R、MWW、FAU、BEA、 CHA，更佳為 MFI、MEL、MOR、MWW、CHA，特佳為 MFI、MEL、 MWW 、 CHA 。 於此，所謂骨架密度（單位T/nm3)，係指每單位體積（lnm3) 沸石中所存在之T原子（構成沸石骨架之原子中，氧以外 的原子）的個數，此值將由沸石之構造所決定。 v 再者，作為該固體酸觸媒，較佳係具有細孔徑為 0· 3〜0· 9nm之微細孔，且BET比表面積為200〜700m2/g， 細孔容積為0· ：1〜0.5g/ml的結晶性鋁矽酸鹽類、金屬相矽 酸鹽（metal losili cate)類或結晶性填酸銘類等。又，此 處所謂細孔徑，係表示由 International Zeolite • Association(IZA)所定之結晶學通道直徑 (Crystallographic free diameter of the channels)， 於細孔（通道）形狀為正圓形時，係指其直徑，於細孔形狀 312XP/發明說明書(補件)/97-01/96135332 23 200831453 為橢圓形時，則指其短徑。 另外，於鋁矽酸鹽中，較佳係Si〇2/Ah〇3之莫耳比為ι〇 以上者。若Si〇2/Al2〇3之莫耳比過低，則由於觸媒的耐久 •性降低，故不佳。Si〇2/Al2〇a莫耳比之上限通常為1〇〇〇〇 -以下。若Si/AhOs之莫耳比較此高’則由於觸媒活性降 ，而不，。上述莫耳比可藉由螢光χ射線和化學分析法等 系法求。 r.„觸媒中之鋁含量可依調製觸媒時之原料裝填量而予以 、控制，又，亦可於調製後藉由蒸氣（steaming)等使A1減 少。又，A1之一部份亦可取代成硼或鎵等其他元素，尤 其以刪取代較佳。 此荨觸媒了單獨使用1種，亦可混合2種以上使用。 本么月中可將上述之觸媒活性成分直接作為觸媒而使 反應中’亦可使用對反應呈惰性之物質和黏著劑，進 行仏粒成型，或混合此等而使用於反應。作為對反應呈 J ?性之物質和黏著劑，可舉例如氧化鋁或氧化鋁凝膠、二 乳化石夕、二氧㈣凝膠、石英及該等之混合物等。 尚j ’上述觸I组成係不含有對此等反應呈惰性之物質 和黏f劑等之僅有觸媒活性成分的組成。因此，本發明中 斤胃觸媒在含有對此等反應呈惰性之物質和黏著劑等 的It况下，係將上述之觸媒活性成分與對此等反應呈惰性 之物貝和黏著劑等合併稱為觸媒，而在不含有對此等反應 呈^ f生之物貝和黏著劑等的情況下，係僅將觸媒活性成分 312XP/發明說明書(補件)/97·〇 1/½ 135332 24 200831453 ^發明所使用之觸媒活性成分 =通了以平徑粒徑計為。.一。二 徑過大，則顯示觸媒活 &quot;右觸媒拉 ，變得差劣，任-情況均w表，料小，右過小則操作性 -等而求得。 句不仏。此平徑粒徑可藉由SEM觀察 本發明所使用之觸姐的击 ^ ^ ^某的凋衣方法並無特別限定，可藉由 -般為熱液合成的公知方法進行調製。 ：：由 亦可藉由離子夺i金 、 ；/夜a成後 Γ、變組成。 、、魅處理、浸含和載持等之修飾而改 性用之觸媒’在供於反應時’若為具有上述物 性及組成即可，而可依任—方㈣以調製。 [反應原料] 其=針對本發明中作為反應原料之碳 烴、甲醇、二甲基醚進行說明。 上之烯 〈烯烴原料〉 G —使用作為反應補之碳數4以上之烯烴，並無限 定。可任意使用例如自石油供給原料藉接觸分解法或蒸氣 裂解等而製造者⑽餾分、C4萃餘液+ 萃餘液—2等、）、、 =煤:炭之氣體化所得之氫/co混合氣體作為原料而進行 (1 sher-Tropsch)合成而得者、藉由含有乙烯之二 ，應之寡聚物化反應所得者、藉由碳數4以上之石峨的脫 虱法或氧化脫氫法所得者、藉_反應所得者、藉 脫水^應所得者、藉由碳數4以上之二稀化合物之氯化反 應所知者等之由公知各種方法所得的碳冑4卩上（尤其是 312XP/發明說明書(補件)/97-01/96135332 200831453 碳數4〜10)之烯烴，此時，可直接使用任意混合了來自於 各製造方法之碳數4以上之烯烴以外之化合物的狀態 者’亦可使用經精製的烯烴。 其中，在使用含有碳數4以上之石蠟類的烯烴原料時， 由於石蠟具有稀釋氣體的效果，故容易控制反應溫度，且 含石蠟的原料可較廉價地取得，故較佳。更佳係含有正丁 烧及異丁烷中之至少一者的烯烴原料。 作為此等較佳原料，可舉例如上述之BB餾分、C4萃餘 D液-1和C4萃餘液-2。此等原料中通常含有丁二烯。由於 丁二烯容易藉由反應而變換為芳香族化合物，故如本發明 般，使所生成之芳香族化合物之至少一部分不回收至反應 器而取出，係屬非常重要。尚且，BB餾分由於含有多量 丁二烯，故較佳係以接觸至氫化觸媒而使丁二烯濃 之流體作為原料者。 一 〈曱醇、二甲基醚&gt; c； 使用作為反應原料之甲醇及二甲基醚中之至少一者的 /製造來源並無特別限定。可舉例如藉由煤碳及天然氣、以 及製鐵業中來自副產物之氫/co混合氣體的氫化反應而得 者；來自植物之醇類之藉改質反應而得者；藉發酵法而得 者；自再循環塑膠和都市廢棄物等之有機物質而得者等。 此時，可直接使用任意混合了來自於各製造方法之甲醇及 二甲基醚以外之化合物的狀態者，亦可使用經精製者。 [反應操作•條件：第卜3態樣中之步驟（1)(lc)] 以下，針對使用上述觸媒及反應原料之本發明之丙烯之 312XP/Mtft^#(ffim/97-〇l/96135332 26 200831453 製造方法的操作•條件進行說明。 〈反應器〉 本^明中’數4以上之烯烴、與曱醇及二曱基鱗中之 至〉、者的反應’係氣相反應。此氣相反應器之形態並無 ，別限制，通常選自連續式之固定床反應器和流動床反應 為。較佳為固定床反應器。 尚且，在將上述觸媒填充至固定床反應器時，為了將觸 p媒層之溫度分佈抑制為較小，故可將石英砂、氧化鋁、二 ^乳化矽、二氧化矽-氧化鋁等之對於反應呈惰性的粒狀物 與觸媒混合再進行填充。此情況下，石英砂等之對反應呈 惰性之粒狀物的使用量並無特別限制。又，由與觸媒之均 勻混合性的觀點而言，此粒狀物較佳係與觸媒相同程度的 粒徑。 另外’反應為亦可為由串聯連接之二個以上反應部所構 成者。此情況下，可將一個反應器内區隔為複數反應室， 亦可為將二個以上之反應器串聯連結者。 ^ &quot; 在如此將二個以上之反應器予以串聯連結時，以去除伴 隨反應所發生之熱的目的下，亦可於反應器與反應器之間 配置熱交換器。 另外’於使發熱分散的目的之下，亦可將反應基質（反 應原料）分割進行供給。較佳係將甲醇及二曱基趟中之至 少一者分割為第1段之反應部（反應器或反應室）與第2段 以後之反應部（反應器或反應室）而進行供給。 本發明中所使用之反應條件中，觸媒係積碳較少、觸媒 312XP/發明說明書(補件)/97-01/96135332 27 200831453 劣化速度慢，但於進行〗年以上之連續運轉的情況下，必 須於運轉中進行觸媒再生。 例如於選擇固疋床反應器時，較佳係至少將二個以上 .反應器並列設置，一邊切換反應與再生而一邊進行運轉。 .作為固定床反應器之形態，係選自多管式反應器或斷熱型 反應器。 另方面，於遥擇流動床反應器時，較佳係將觸媒連續 性地送至再生槽，將於再生槽中所再生之觸媒連續性地送 C 回至反應器進行反應。 於此，作為觸媒之再生操作，可舉例如將因積碳而劣化 的觸媒’藉由含有氧之氮氣體和水蒸氣等進行處理而再生 =方法。作為固定床反應器中之再生操作，較佳係利用氮 氣體將附著於觸媒上之揮發性有機化合物去除後，以含有 低濃度氧之氮氣體將焦煤份予以燃燒去除，其後，以^氣 體進行處理，藉此將觸媒層中所含之分子狀氧去除的= 法。 f 〈供給至反應器之烯烴與曱醇及二甲基醚中之 濃度比〉 考的 本發明中，供給至反應器中之碳數4以上之烯烴 係相對於供給至反應器中之甲醇莫耳數與二曱基| 數2倍的合計，以莫耳比計為〇·2以上、較佳〇·%以上， 並為10以下、較佳5以下。 · ’ 312XP/發明說明書(補件)/97-01/96135332 28 200831453 設為Mdm時，Mc4為（Mm+2Mdm)之0· 2〜10倍、較佳 倍0 不論此供給濃度比過低或過南’反應均變慢而不佳，尤 其疋，右此供給丨辰度比過低，則將減少原料婦煙的消耗 量，故不佳。 於此，供給濃度比係可藉由將分別供給至反應器之流體 或混合後之流體的組成，以氣相層析法等之一般分析手法 進行定量而得知。 尚且，在將碳數4以上之烯烴、與甲醇及二甲基醚中之 至少一者供給至反應器時，可將此等分別供給，亦可預先 將一部分或全部混合後再供給。 〈供給至反應器之基質濃度&gt; 本發明中，供給至反應器之總供給原料中，碳數4以上 之烯烴與甲醇及二甲基醚的合計濃度（基質濃度），較佳為 20體積％以上、80體積％以下，更佳為3〇體積％以上、7〇 〇 體積％以下。 、於此’基請度係可藉由將分別供給至反應器之流體或 混合後之流體的組成’以氣相層析法等之一般分析手法進 行定量而得知。 右此基質濃度過高，則芳香族彳卜人 万0秩化合物和石蠟類的生成變 得顯著，而有丙烯之選擇率降低的 ，&quot;命、“低的傾向。相反地，若此基 貝浪度過低，則由於反應速度變愣 〇 ^ ^ ^ H ^ Γ又’故需要大量的觸媒， 且生成物之精製成本和反應設備 1用幻建设費亦增大，而不經 濟0 312ΧΡ/發明說明書(補件)/97-〇1/96135332 200831453 本發明中，係以下述所 Ά ^ ^ ^ 17裁之稀釋氣體將反應基質稀釋 下作為控制基質濃度的方法， 可舉例如控制自製程取出之流曰 t ^ 〜'巩篮流夏的方法。亦即，Μ出 改變自製程取出之流體流量， 曰 氣體的流量變化，而改變基質濃1收至反應…稀釋 〈供給至反應器之氣體中的雜質濃度〉C, better 9°, and more excellent [catalyst] First, the catalyst used in the present invention will be described. (:B (3⁄4 is the catalyst used for the reaction of the month, if it is a solid Zhao-like character with i-rr:dsite), there is no special limit. Such as clay minerals; sulfuric acid, phosphoric acid on the carrier of two soil minerals; acid type ion 乂 树 曰 曰 曰, fossils; aluminum phosphate; Α M MCM41 and other mesoporous 312XP / invention manual ( Replenishment) /97·〇ι/96〗35332 200831453 (mesoporous) Separate solid oxide catalyst such as cerium oxide oxidized. Such solid acid catalysts are preferably those having molecular sieve effect, and preferably In the solid acid catalyst, the structure of zeolites and phosphoric acid having a molecular sieve effect, as indicated by the code defined by the International Zeolite Association (IZA), may be, for example, ruthenium or osmium. AEL, AFI, AF0, AFS, AST, ΑΤΝ, ΒΕΑ, CAN, CHA, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, Γ' MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON, etc., wherein the preferred catalyst has a skeletal density of 18. OT/nm3 The catalyst, as such, preferably, for example, MFI, MEL, MOR, MWW, FAU, BEA, CHA, more preferably MFI, MEL, MOR, MWW, CHA, especially MFI, MEL, MWW, Here, the skeletal density (unit: T/nm3) means the number of T atoms (atoms other than oxygen in the atoms constituting the zeolite skeleton) present in the zeolite per unit volume (lnm3), and this value will be Further, as the solid acid catalyst, it is preferable to have fine pores having a pore diameter of 0·3 to 0·9 nm, and a BET specific surface area of 200 to 700 m 2 /g, and a pore volume of 0· : 1 to 0.5 g/ml of crystalline aluminosilicates, metal losili cates, or crystalline acid-filled ingots, etc. Here, the pore diameter is represented by International. The crystallographic free diameter of the channels defined by Zeolite • Association (IZA), when the pores (channels) are in the shape of a perfect circle, refer to the diameter of the pores in the shape of the pores 312XP / invention instructions (repair) ) /97-01/96135332 23 200831453 When it is elliptical, it means its short diameter. In addition, the aluminum silicate, the preferred system Si〇2 / Ah〇3 ι〇 the molar ratio or more. If the molar ratio of Si〇2/Al2〇3 is too low, the durability of the catalyst is lowered, which is not preferable. The upper limit of the Si〇2/Al2〇a molar ratio is usually 1 〇〇〇〇 - or less. If the Mo of Si/AhOs is higher than this, then the activity of the catalyst is lowered, no. The above molar ratio can be obtained by a method such as fluorescent ray irradiation and chemical analysis. r. The aluminum content in the catalyst can be controlled and controlled according to the amount of raw materials used to prepare the catalyst. In addition, after the preparation, the A1 can be reduced by steaming, etc. It can be replaced by other elements such as boron or gallium, and it is preferable to use it as a substitute. This catalyst can be used alone or in combination of two or more. The above-mentioned catalyst active ingredient can be directly used as a touch. In the reaction, the substance and the adhesive which are inert to the reaction may be used in the reaction, or the mixture may be formed into a mixture, or may be used in the reaction. As a substance and an adhesive which is responsive to the reaction, for example, oxidation may be employed. Aluminum or alumina gel, diacetate, dioxane (tetra) gel, quartz, and mixtures thereof, etc. The above-mentioned touch I composition does not contain substances inert to such reactions and adhesion agents. It has only the composition of the active ingredient of the catalyst. Therefore, in the case of the present invention, the active substance of the catalyst is reacted with the above-mentioned catalyst active ingredients in the case of a substance containing an inert substance and an adhesive. Inert materials such as shells and adhesives are called catalysts. In the case where there is no such thing as the shell and the adhesive, the catalyst active ingredient 312XP/invention specification (supplement)/97·〇1/1⁄2 135332 24 200831453 ^invented The catalyst active ingredient used = is measured by the diameter of the flat diameter. 1. When the two paths are too large, the catalyst activity is displayed, and the right catalyst is pulled, which is inferior. Small, the right is too small, the operability - etc. is obtained. The diameter of the flat diameter can be observed by SEM observation of the use of the touch of the sister of the invention is not particularly limited, Modulation is carried out by a known method for hydrothermal synthesis. :: It can also be modified by ions, or formed by the formation of ions, immersion and support. Further, the catalyst for the modification "in the case of the reaction" may have the above physical properties and composition, and may be prepared according to the formula (4). [Reaction raw materials] It is a hydrocarbon hydrocarbon as a reaction raw material in the present invention. Methanol and dimethyl ether are described. The above olefins (olefin raw materials) G - the use of olefins having a carbon number of 4 or more as a reaction, There is no limitation. For example, a hydrogen obtained by gasification of carbon can be produced by a producer (10) fraction, a C4 raffinate + a raffinate, etc., from a petroleum feedstock by contact decomposition or steam cracking. The /co mixed gas is synthesized as a raw material (1 sher-Tropsch), obtained by the oligomerization reaction containing ethylene, and desulfurized or oxidized by a cerium having a carbon number of 4 or more. Those obtained by the dehydrogenation method, those obtained by the reaction, those obtained by dehydration, those known by the chlorination reaction of a divalent compound having a carbon number of 4 or more, etc., which are obtained by various known methods ( In particular, 312XP/invention specification (supplement)/97-01/96135332 200831453 olefin having a carbon number of 4 to 10), in which case, a compound other than the olefin having 4 or more carbon atoms derived from each production method may be used as it is. The state of the art can also use refined olefins. Among them, when an olefin raw material containing a paraffin having a carbon number of 4 or more is used, since the paraffin has an effect of diluting a gas, it is easy to control the reaction temperature, and a paraffin-containing raw material can be obtained at a relatively low cost, which is preferable. More preferably, it is an olefin raw material containing at least one of n-butylene and isobutane. As such preferred raw materials, for example, the above-mentioned BB fraction, C4 raffinate D liquid-1 and C4 raffinate-2 can be mentioned. These materials usually contain butadiene. Since butadiene is easily converted into an aromatic compound by a reaction, it is very important that at least a part of the produced aromatic compound is not recovered in the reactor and taken out as in the present invention. Further, since the BB fraction contains a large amount of butadiene, it is preferred to use a fluid having a butadiene concentration as a raw material in contact with a hydrogenation catalyst. 1. The decyl alcohol, dimethyl ether &gt;c; The source of the use of at least one of methanol and dimethyl ether as a reaction raw material is not particularly limited. For example, it can be obtained by a hydrogenation reaction of coal and natural gas, and a hydrogen/co mixed gas derived from by-products in the iron industry; a plant-derived alcohol is obtained by a modification reaction; Those who have obtained organic substances such as recycled plastics and municipal wastes. In this case, any one of a state in which a compound other than methanol or dimethyl ether from each production method is mixed may be used as it is, and a purified one may be used. [Reaction operation and conditions: Step (1) (lc) in the third aspect] Hereinafter, the 312XP/Mtft^# of the propylene of the present invention using the above catalyst and reaction raw material (ffim/97-〇l/) 96135332 26 200831453 The operation and conditions of the manufacturing method are explained. <Reactor> The reaction of '4 or more olefins with sterols and diterpene scales> is the gas phase reaction. The form of the gas phase reactor is not limited, and is usually selected from a continuous fixed bed reactor and a fluidized bed reaction, preferably a fixed bed reactor. Further, when the catalyst is filled into a fixed bed reactor, In order to suppress the temperature distribution of the n-touch layer to be small, the granular material which is inert to the reaction, such as quartz sand, alumina, emulsified cerium, cerium oxide-alumina, etc., may be mixed with the catalyst. In this case, the amount of the granular material which is inert to the reaction such as quartz sand is not particularly limited. Further, from the viewpoint of uniform mixing with the catalyst, the granular material is preferably bonded. The catalyst has the same degree of particle size. In addition, the reaction can also be connected by series. Two or more reaction units are formed. In this case, one reactor may be partitioned into a plurality of reaction chambers, or two or more reactors may be connected in series. ^ &quot; When the above reactors are connected in series, a heat exchanger may be disposed between the reactor and the reactor for the purpose of removing heat generated by the reaction. Further, the purpose of dispersing heat may be The reaction substrate (reaction raw material) is divided and supplied. Preferably, at least one of methanol and dimercaptopurine is divided into a reaction portion (reactor or reaction chamber) of the first stage and a reaction unit after the second stage (reaction) In the reaction conditions used in the present invention, the catalytic carbon is less, and the catalyst 312XP/invention specification (supplement)/97-01/96135332 27 200831453 has a slow deterioration rate, but In the case of continuous operation for more than one year, it is necessary to carry out catalyst regeneration during operation. For example, when selecting a solid-state reactor, it is preferable to set at least two or more reactors in parallel while switching the reaction and regeneration. While operating as a fixed bed reactor, it is selected from a multi-tubular reactor or a heat-dissipating reactor. On the other hand, in the case of a remote selective fluidized bed reactor, it is preferred to continuously contact the catalyst. The catalyst is sent to the regeneration tank, and the catalyst regenerated in the regeneration tank is continuously sent back to the reactor for reaction. Here, as the catalyst regeneration operation, for example, a catalyst which deteriorates due to carbon deposition may be mentioned. The regeneration is carried out by treatment with a nitrogen gas containing oxygen and steam, etc. As a regeneration operation in the fixed bed reactor, it is preferred to remove the volatile organic compound attached to the catalyst by using a nitrogen gas to contain The low-concentration oxygen nitrogen gas is burned and removed, and then treated with a gas to remove the molecular oxygen contained in the catalyst layer. f <concentration ratio of olefin to decanol and dimethyl ether supplied to the reactor> In the present invention, the amount of olefins having a carbon number of 4 or more supplied to the reactor is relative to the methanol supplied to the reactor The total number of ears and the number of diterpene groups is 2 times, and the molar ratio is 〇·2 or more, preferably 〇·% or more, and is 10 or less, preferably 5 or less. · ' 312XP / Invention Manual (Repair) / 97-01/96135332 28 200831453 When Mdm is set, Mc4 is 0· 2~10 times (Mm+2Mdm), preferably 0 times, regardless of the supply concentration ratio is too low or The over-south's reaction is slower and slower, especially 疋. If the ratio of the supply to the right is too low, the consumption of raw materials will be reduced, so it is not good. Here, the supply concentration ratio can be known by quantifying the composition of the fluid supplied to the reactor or the mixed fluid by a general analytical method such as gas chromatography. Further, when at least one of the olefin having 4 or more carbon atoms and methanol and dimethyl ether is supplied to the reactor, these may be supplied separately, or a part or all of them may be mixed beforehand and supplied. <Base concentration to be supplied to the reactor> In the present invention, the total concentration (base concentration) of the olefin having a carbon number of 4 or more and methanol and dimethyl ether in the total supply raw material supplied to the reactor is preferably 20 volumes. More than or equal to 80% by volume, more preferably 3% by volume or more and 7% by volume or less. The basis of this can be determined by quantifying the composition of the fluid supplied to the reactor or the composition of the mixed fluid by a general analytical method such as gas chromatography. When the concentration of the matrix on the right is too high, the formation of the aromatic oxime and the paraffin wax becomes remarkable, and the selectivity of propylene decreases, and the tendency of "low" tends. On the contrary, if the base is When the Bayer wave is too low, the reaction speed becomes 愣〇^^^H^ Γ and then a large amount of catalyst is required, and the refining cost of the product and the magical construction fee of the reaction device 1 are also increased, and it is not economical. 312ΧΡ/发明发明(补件)/97-〇1/96135332 200831453 In the present invention, the reaction substrate is diluted as a method for controlling the concentration of the substrate by using a diluent gas as described below, for example, control is carried out. The process of taking out the flow t ^ ~ 'the process of the basket flow summer. That is, the flow rate of the fluid taken out by the self-made process is changed, the flow rate of the helium gas changes, and the concentration of the substrate is changed to the reaction... dilution is supplied to the reactor Impurity concentration in the gas>

C 本發明中，有時有碳數4以上之又烯烴原料中仏戈所回 收之後述之含烴流體中含有丁二烯的情形，而作為供哈至 。反應器Λ之總供給原料的了二烯濃度，較料2.0體積 /以下。若原料中之丁一嫌、、麄 一 ^ 、 、“ T T j 一佈/辰度過咼，則芳香族化合物之 生成將增加，且因觸媒之積碳所造成的劣化變快，故不佳。 、於此丁一烯/辰度係可藉由將分別供給至反應器之流體 或混合後之流體的組成，以氣相層析法等之一般分析手法 進行定量而得知。 作為使原料中之丁二烯濃度降低的方法，可舉例如將該 流體與氫化觸媒接觸而變換為烯烴類的部分氫化法。^ 另外，有時有回收至反應器之後述含烴流體中含有芳香 族^合物的情形，而作為供給至反應器中之總原料中的二 香族化合物的合計量，係相對於供給至反應器中之總原料 中所含的碳數4以上之烯烴的合計量，以莫耳比計為未滿 〇· 05。若原料中之芳香族化合物濃度過高，則於反應器 内，芳香族化合物與碳數4以上之烯烴之反應、和芳香族 化合物與曱醇及二曱基醚中之至少一者的反應變得顯 著’將非必要地消耗碳數4以上之烯烴與甲醇及二甲基鍵 312ΧΡ/發明說明書(補件)/97-01/96135332 30 200831453 中之至少一者，故不佳。 述香族化合物供給至反應器時，由於因與上 Ί '之稀經的反應中所生成之化合物將使觸媒 ，口流體中之芳香族化合物從系統内取出== 反應器之流體中的芳香族化合物濃度降低。收至 於此上述芳香無化合物之合計量與碳數4以上之炉 之合計量的比，係可藉由將分別供給： =之流㈣組成，以氣相層析法等之—般分析 疋置而得知。 作為使原财之芳香族化合㈣度降低的方法，可舉 如蒸餾所進行的分離法。 〈稀釋氣體〉 於反應器内，除了碳數4以上之烯烴、與甲醇及二甲基 ，中’，少-者以外，亦可存在石躐類、芳香族類、水蒸 ^、二氧化碳、一氧化碳、氮、氬、氦、及此等之混合物 般,對反應呈惰性的氣體。又，此等稀釋氣體中，石蠟類 和芳香族類，係視反應條件而進行少許反應，由於反應量 少’故定義為稀釋氣體。 作為此種稀釋氣體，可直接使用反應原料中所含之雜 質，亦可將另外調製之稀釋氣體與反應原料混合使用。 另外，稀釋氣體可於置入反應器前先與反應原料混合， 亦可與反應原料分開供給至反應器。 作為較佳之稀釋氣體，為碳數4以上之石犧類。更佳係 312XP/發明說明書(補件)/97-01/96135332 31 200831453 正丁烧及異丁烧之至少一者。此等石蠛類 料中所含者，並由於屬於熱容量大的物可：烯煙原 反應溫度。 ）化。物，故容易控制 〈空間速度〉 於此所謂的空間速度，係指每單位重量觸媒（觸媒活性 成分）之屬於反應原料之碳數4以上之烯烴的流量，於 此，觸媒重量係指不包含使用於觸媒造粒·成型之，产性 分和黏著劑的觸媒活性成分之重量。χ，流量係碳^以 上之細煙之流量（重量/時間）。 空間速度較佳為O.lHr1至500ΗΓ1之間，更佳i 〇 jjf 至100 Hr—1之間。若空間速度過高，則原料之烯烴與曱l 及二：基醚中之至少一者的轉化率變低，且無法得到充分 的丙烯選擇率。又，若空間速度過低，則為了得到一定的 生產量，所需之觸媒量變多，而使反應器變得過大，且會 生成芳香族化合物和石蠟等之不佳的副產物，丙烯選擇^ 降低，故不佳。In the present invention, in the case where the carbonaceous material having a carbon number of 4 or more is recovered from the olefinic material, the hydrocarbon-containing fluid described later contains butadiene. The diene concentration of the total feedstock of the reactor was 2.0 v/min. If the raw materials in the raw materials are smack, 麄一^, and "TT j a cloth/times pass, the formation of aromatic compounds will increase, and the deterioration caused by the carbon deposition of the catalyst will become faster. Preferably, the butylene/Chen degree system can be obtained by quantifying the composition of the fluid supplied to the reactor or the mixed fluid by a general analytical method such as gas chromatography. The method of reducing the concentration of butadiene in the raw material may be, for example, a partial hydrogenation method in which the fluid is brought into contact with a hydrogenation catalyst to be converted into an olefin. In addition, there may be a case where the hydrocarbon-containing fluid is contained in the reactor after being recovered. In the case of a family compound, the total amount of the diaromatic compound in the total raw material supplied to the reactor is the total of the olefins having 4 or more carbon atoms contained in the total raw material supplied to the reactor. The amount is not more than 莫· 05 in terms of molar ratio. If the concentration of the aromatic compound in the raw material is too high, the reaction of the aromatic compound with the olefin having 4 or more carbon atoms in the reactor, and the aromatic compound and hydrazine At least one of an alcohol and a dimethyl ether The reaction becomes remarkable. It is not necessary to consume at least one of the olefin having a carbon number of 4 or more and the methanol and the dimethyl bond 312 ΧΡ / invention specification (supplement) / 97-01/96135332 30 200831453. When the aromatic compound is supplied to the reactor, the aromatic compound in the oral fluid is taken out of the system due to the catalyst formed by the reaction with the thinning of the upper sputum, and the aromatics in the fluid of the reactor are removed. The concentration of the compound is lowered. The ratio of the total amount of the aromatic compound-free compound to the total amount of the furnace having a carbon number of 4 or more can be obtained by separately supplying: = stream (4), by gas chromatography or the like. As a method of reducing the degree of aromatic compounding (four degrees) of the original money, a separation method by distillation may be mentioned. <Diluted gas> In the reactor, in addition to the olefin having 4 or more carbon atoms, In addition to methanol and dimethyl, in the middle, and less, there may also be a mixture of sarcophagi, aromatics, water vapor, carbon dioxide, carbon monoxide, nitrogen, argon, helium, and the like. Inert gas. Again, this In the gas release, paraffin and aromatics are slightly reacted depending on the reaction conditions, and are classified as a diluent gas because of a small amount of reaction. As such a diluent gas, impurities contained in the reaction raw material may be used as they are. The separately prepared diluent gas is mixed with the reaction raw material. Further, the diluent gas may be mixed with the reaction raw material before being placed in the reactor, or may be supplied to the reactor separately from the reaction raw material. As a preferred diluent gas, the carbon number is 4 The above stone sacrifice class. Better 312XP / invention manual (supplement) /97-01/96135332 31 200831453 At least one of the diced and diced. The inclusion of these sarcophagus materials, and because The material having a large heat capacity can be: the reaction temperature of the olefinic nicotinic acid, and it is easy to control the space velocity. The space velocity referred to herein refers to the reaction material per unit weight of the catalyst (the active component of the catalyst). The flow rate of the olefin having a carbon number of 4 or more, the catalyst weight means the weight of the catalytically active component which is used for the granulation and molding of the catalyst, and the yield and the adhesive. χ, the flow rate is the flow rate of the fine smoke (weight/time). The space velocity is preferably between 0.1Hr1 and 500ΗΓ1, more preferably between i 〇 jjf and 100 Hr-1. When the space velocity is too high, the conversion ratio of at least one of the olefin of the raw material and the hydrazine and the dimethyl ether is lowered, and a sufficient propylene selectivity cannot be obtained. Further, when the space velocity is too low, in order to obtain a constant throughput, the amount of catalyst required is increased, and the reactor is excessively large, and undesirable by-products such as aromatic compounds and paraffin are formed, and propylene is selected. ^ Reduced, so it is not good.

U 〈反應溫度〉 反應溫度之下限，以反應器入口之氣體溫度計，通常為 約300°C以上、較佳4〇(rc以上，反應溫度之上限，通常 為700°C以下、較佳6〇〇t：以下。若反應溫度過低，則反 應速度低’而有較多地殘留未反應原料的傾向，而且丙烯 的產率亦降低。另一方面，反應溫度若過高，則丙烯與產 率會顯著降低。 〈反應壓力〉 312XP/發明說明書(補件)/97-01/96135332 32 200831453 1反應壓力之上限通常為2MPa(絕對壓，以下亦同）以下、 較佳IMPa以下、更佳〇.7MPa以下。又反應壓力之下限 並無特別限制，通常為lkPa以上、較佳5〇咖以上。若 •反應壓力過高，則石_和芳香族化合物等之不佳副產物 .的生成量增加，而有丙烯產率降低的傾向。若反應壓力過 低，則有反應速度變慢的傾向。 〈反應之原料消耗量〉 相對於供給至反應器之甲醇之莫耳流量與二曱基醚之 (莫耳流量2倍的合計，反應器出口之甲醇之莫耳流量與二 曱基醚之莫耳流量2倍的合計較佳為未滿1%、更佳未滿 0· 10/〇 〇 若反應器中之甲醇及二甲基㈣消耗量少，而反應器出 口之曱醇及二甲基醚之量增加，則製品烯烴的精製變得困 難。 作為使曱醇及二曱基醚之消耗量增多的方法’可舉例如 提升反應溫度、降低空間速度之方法。 。 另外，本發明中，相對於供給至反應器之碳數4以上之 烯烴的莫耳流量，將反應器出口之碳數4以上之烯烴的莫 耳流置設為20%以上、未滿90%。此莫耳流量比例較佳為 20%以上、未滿70%、更佳為25%以上、未滿_。若反應 裔中之奴數4以上之烯烴之消耗量過少，則未反應的烯烴 -變多，回收至反應器之流體流量將變得過大，故不佳。相 反地，若消耗量過多，則將副產生出石蠟和芳香族化合物 等不佳化合物，丙烯產率降低，故不佳。 312XP/發明說明書(補件)/97-01/96135332 33 200831453 作為凋整反應器中之碳數4以上之烯烴之消耗量的方 法，可舉例如適當地設定反應溫度和空間速度等之方法。 在此，供給至反應器之甲醇與二甲基醚及碳數4以上之 烯煜的々,L里，可對供給至反應器之各流體或混合後流體之 組成，以氣相層析法等一般分析手法進行定量，測定各流 體之流量便可知，反應器出口之曱醇與二甲基鍵及碳數4 以上之烯烴的流量，可利用氣相層析法等一般手法，對反 應器出口流體之組成進行定量，測定或計算反應器出口流 f 體之流量便可知。 〈反應生成物〉 作為反應器出口氣體（反應器流出物），可得到含有屬於 反應生成物之丙烯、未反應原料、副產物及稀釋劑的混合 氣體。該混合氣體中之丙烯濃度通常為5〜95重量％。 未反應原料通常為碳數4以上之烯烴。視反應條件雖含 有曱醇及二曱基醚中之至少一者，但較佳係依使曱醇及二 曱基醚中之至少一者不殘留的反應條件進行反應。藉此二 U可容易分離反應生成物與未反應原料。 作為副產物，可舉例如乙烯、碳數4以上之稀煙類、石 蠟類、芳香族化合物及水。 [分離步驟] * {第1及第2態樣中之分離步驟} ，〈碳數3以下之烴及水的分離：步驟（2)&gt; 反應器出口氣體係藉由冷卻、壓縮及蒸餾等之一般分離 步驟’为離為虽含碳數3以下之經的流體、富含碳數4以 312XP/發明說明書(補件)/97-01/96135332 34 200831453 上之烴的流體（A)、及富含水之流體。 作為上述一般之分離步驟的筮 的弟1態樣，可適用含有下诚 步知的方法：藉冷卻及壓縮歩驟 ^ # \ 、 唯步驟將水分凝縮去除後，藉1 备为離為昌含碳數2以下之烴^、、六 、、、 〜&amp;的/爪體與富含碳數3以上之 烴的流體，將富含碳數3以上之栌沾士触抓 工（度的流體藉蒸餾分離為舍 含碳數3之烴的流體與富含碳數4以上之烴的流體（a)。田 作為-般之分離步驟的第2態樣，可適用含有下述步驟 的方法.藉冷卻及壓縮步㈣水分凝縮去除後，藉蒸餘分 離為富含碳數3以下之烴的流體與富含碳數4以上之煙的 流體（A)’將富含碳數3以下之烴的流體藉蒸餾分離為富 含碳數2以下之烴的流體與富含碳數3之烴的流體。 作為一般之分離步驟的第3態樣，可適用含有下述步驟 的方法：藉冷卻及壓縮步驟將水分凝縮去除後，藉蒸餾分 離2富含碳數2以下之烴的流體與富含碳數3之烴的流體 與富含碳數3以上之烴的流體，將富含碳數3以上之烴的 流體藉蒸餾分離為富含碳數3之烴的流體、富含碳數4以 上之烴的流體（A)。 作為上述一般之分離步驟的第4態樣，可適用含有下述 步驟的方法：藉冷卻及壓縮步驟將水分凝縮去除後，藉蒸 备为離為畐含碳數3以下之烴的流體與富含碳數4以上之 煙的流體（A)，將富含碳數3以下之烴的流體藉蒸餾分離 為萄含碳數2以下之烴與碳數3之烴的流體與富含碳數3 之烴的流體。 上述一般分離步驟之第1〜第4態樣中，視需要較佳為 312XP/發明說明書(補件)/97-01/96135332 35 200831453 進行淬火、驗洗淨、脫水等之卢 中含有含氧化合物的情況下由:^於反應器出口氣體 一邱八夕人人你. 猎由泠火步驟，將去除至少 刀之含虱化合物。在於反應器 •碳等之酸性氣體的情況下，_由p /、_中3有二乳化 .分之酸性氣體。 冑仏切’將去除至少-部 水之分離主要可藉由壓縮與冷卻進行凝縮。 較佳係以分子篩等之吸附劑進— ’、 而去除的水可供於活性污泥等 飞 Γ於製程水。 廢水處理步驟，亦可使用 f二發= 3(1下有時稱為「本製程」)為接近蒸氣 衣解衣矛壬的情況下，自反應界出名 ,,,ffl . ^ 出口軋體所回收的水較佳係 利用作為表解之瘵氣源。又，亦可 中使用作為稀釋氣體。 口收至本製程之反應器 ，外’自反應H出口氣體所得之碳數2以下的烴 =，更佳係藉由蒸顧等之精製步驟所得之高純 G :::。作為乙烯之純度，梅乂上、較請以上。 =為以上。作為丙烯之純度為95%以上、較請 以上。更佳99· 9%以上。 如此所得之乙烯及丙浠，即使由雜質量等之品質性觀點 :言，亦可使用作為—般所製造之乙稀及㈣衍生物的原 料，例如乙婦可使用於藉由氧化反應而製造環氧乙烧、乙 .广乙醇胺、二_等，藉由氯化而製造氯化乙烯基單 -、1’1，卜二氯乙烧、氯化乙婦樹脂、偏二氯乙烯，或藉 由乙烯聚合而製造“烯烴、低密度或高密度之聚乙烯，藉 312XP/發明說明書(補件)/97-01/96135332 36 200831453 本之乙基化而製造乙基苯等。 由乙烯所製造之乙二醇’可進—步將其作為原料而 3對苯二曱酸乙二自旨’烯烴作為原料並藉由側氧基反 次之氫化反應而製造高級醇，將乙基苯作為原料而 ::本乙烯單體、ABS樹脂等。χ，藉由與醋酸之反應亦 了 ：造醋酸乙烯酯’藉由瓦克(Wacker)反應亦可製造：醛 及屬於其之衍生物之醋酸乙酯等。U <Reaction temperature> The lower limit of the reaction temperature, the gas thermometer at the inlet of the reactor, is usually about 300 ° C or higher, preferably 4 〇 (rc or more, the upper limit of the reaction temperature, usually 700 ° C or lower, preferably 6 〇). 〇t: the following. If the reaction temperature is too low, the reaction rate is low, and there is a tendency for more unreacted raw materials to remain, and the yield of propylene is also lowered. On the other hand, if the reaction temperature is too high, propylene is produced. The reaction rate is significantly lower. <Reaction pressure> 312XP/Invention manual (supplement)/97-01/96135332 32 200831453 1 The upper limit of the reaction pressure is usually 2 MPa (absolute pressure, the same applies hereinafter), preferably less than 1 MPa, more preferably 7. 7 MPa or less. The lower limit of the reaction pressure is not particularly limited, and is usually 1 kPa or more, preferably 5 Å or more. If the reaction pressure is too high, the formation of poor by-products such as stone _ and aromatic compounds. When the amount is increased, the yield of propylene tends to decrease. If the reaction pressure is too low, the reaction rate tends to be slow. <Resource consumption of the reaction> The molar flow rate of methanol relative to the methanol supplied to the reactor Ether The total of the flow rate is 2 times, and the total of the molar flow rate of methanol at the outlet of the reactor and the molar flow rate of the dimercapto ether is preferably less than 1%, more preferably less than 0·10/〇〇 in the reactor. The consumption of methanol and dimethyl (tetra) is small, and the amount of decyl alcohol and dimethyl ether at the outlet of the reactor increases, which makes it difficult to refine the olefin of the product. As the consumption of decyl alcohol and didecyl ether increases. The method 'is, for example, a method of raising the reaction temperature and lowering the space velocity. Further, in the present invention, the carbon number of the outlet of the reactor is 4 or more with respect to the molar flow rate of the olefin having 4 or more carbon atoms supplied to the reactor. The molar flow rate of the olefin is set to be 20% or more and less than 90%. The molar flow ratio is preferably 20% or more, less than 70%, more preferably 25% or more, and less than _. If the consumption of olefins having a slave number of 4 or more is too small, the amount of unreacted olefins will increase, and the flow rate of the fluid recovered to the reactor will become too large, which is not preferable. Conversely, if the amount of consumption is too large, paraffin will be produced by the side. As a poor compound such as an aromatic compound, the yield of propylene is lowered, which is not preferable. 12XP/Invention Manual (Supplement)/97-01/96135332 33 200831453 As a method of consuming the amount of olefin having 4 or more carbon atoms in the reactor, for example, a method of appropriately setting the reaction temperature and the space velocity can be mentioned. Here, the methanol, the dimethyl ether and the olefin having a carbon number of 4 or more are supplied to the reactor, and the composition of the fluid supplied to the reactor or the mixed fluid can be obtained by gas chromatography. When the flow rate of each fluid is measured by a general analysis method, the flow rate of the sterol and the dimethyl bond and the olefin having a carbon number of 4 or more at the outlet of the reactor can be determined by a general method such as gas chromatography or the like. The composition of the outlet fluid is quantified, and the flow rate of the reactor outlet stream f is measured or calculated. <Reaction product> As a reactor outlet gas (reactor effluent), a mixed gas containing propylene, an unreacted raw material, a by-product, and a diluent belonging to the reaction product can be obtained. The concentration of propylene in the mixed gas is usually from 5 to 95% by weight. The unreacted raw material is usually an olefin having 4 or more carbon atoms. Although the reaction conditions include at least one of decyl alcohol and didecyl ether, it is preferred to carry out the reaction under reaction conditions in which at least one of decyl alcohol and dimethyl ether is not left. Thereby, the reaction product and the unreacted raw material can be easily separated by the two U. Examples of the by-products include ethylene, a rare carbon having 4 or more carbon atoms, a paraffin wax, an aromatic compound, and water. [Separation step] * {Separation step in the first and second aspects}, "Separation of hydrocarbons and water having a carbon number of 3 or less: Step (2) &gt; Reactor outlet gas system by cooling, compression, distillation, etc. The general separation step 'is a fluid (A) having a carbon number of 3 or less, a hydrocarbon having a carbon number of 4 to 312XP/invention specification (supplement)/97-01/96135332 34 200831453, And water-rich fluids. As a mode of the above-mentioned general separation step, it is possible to apply a method including the following steps: by cooling and compressing the enthalpy ^ #, and only after the step of removing the moisture condensation, borrowing 1 is prepared for the inclusion of Hydrocarbons having a carbon number of 2 or less, /, and / / of a fluid having a carbon number of 3 or more, and a fluid having a carbon number of 3 or more Divided into a fluid containing a hydrocarbon having a carbon number of 3 and a fluid (a) having a hydrocarbon having a carbon number of 4 or more. As a second aspect of the separation step, the method comprising the following steps can be applied. After the water condensation is removed by the cooling and compression steps (4), the fluid separated by the steam residue into a hydrocarbon having a carbon number of 3 or less and the fluid having a carbon number of 4 or more (A)' will be rich in hydrocarbons having a carbon number of 3 or less. The fluid is separated by distillation into a fluid rich in hydrocarbons having a carbon number of 2 or less and a fluid having a hydrocarbon having a carbon number of 3. As a third aspect of the general separation step, a method comprising the steps of: cooling and After the condensation step removes the moisture condensation, the fluid rich in carbon number 2 or less and the carbon-rich number 3 are separated by distillation. a fluid and a fluid rich in carbon atoms of 3 or more, and a fluid rich in carbon atoms of 3 or more is separated into a fluid rich in carbon number 3 and a fluid rich in hydrocarbons having 4 or more carbons by distillation ( A) As a fourth aspect of the above-described general separation step, a method comprising the steps of: condensing and removing water by a cooling and compression step, and then distilling it into a hydrocarbon having a carbon number of 3 or less The fluid and the fluid (A) rich in carbon 4 or more smoke are separated from the fluid having a carbon number of 3 or less by distillation into a fluid having a carbon number of 2 or less and a hydrocarbon having 3 carbon atoms and rich in The fluid of the hydrocarbon having a carbon number of 3. In the first to fourth aspects of the above general separation step, if necessary, it is preferably 312XP/invention specification (supplement)/97-01/96135332 35 200831453 for quenching, washing, and In the case of dehydration, etc., in the case of oxygen-containing compounds: ^ in the reactor outlet gas, Qiu Qixi, everyone. Hunting by the bonfire step, will remove at least the ruthenium-containing compound of the knife. It depends on the reactor, carbon, etc. In the case of acid gas, _ is emulsified by p /, _ 3, and is divided into acid gases. The separation of the at least part of the water is mainly condensed by compression and cooling. It is preferred that the water removed by the adsorbent such as molecular sieve can be used to fly the activated sludge or the like to the process water. In the case of f-fat = 3 (sometimes referred to as "this process" in 1 time), it is known as the spoiler from the reaction, and ffl. ^ is recovered from the export rolling body. The water is preferably used as a helium gas source for the solution. In addition, it can also be used as a diluent gas. The reactor is received in the process, and the hydrocarbon having a carbon number of 2 or less from the reaction gas of the reaction H is more The high purity G::: obtained by steaming and other purification steps is used as the purity of ethylene. = is above. The purity of propylene is 95% or more, which is more than the above. More preferably 99.9% or more. The ethylene and propylene carbonate thus obtained can be used as a raw material of ethylene and (tetra) derivatives which are generally produced, for example, from the viewpoint of quality of impurities, etc., for example, it can be used for production by oxidation reaction. Ethylene bromide, B. ethanolamine, bis, etc., by chlorination to produce vinyl chloride mono-, 1 '1, dichloroethane, chlorinated ethylene resin, vinylidene chloride, or borrow Ethylene, low-density or high-density polyethylene is produced by polymerization of ethylene, and ethylbenzene is produced by ethylation of 312XP/invention specification (supplement)/97-01/96135332 36 200831453. Ethylene glycol can be used as a raw material and 3-p-benzoic acid is used as a raw material, and a higher alcohol is produced by a hydrogenation reaction of a sideoxy group, and ethylbenzene is used as a raw material. And:: the present ethylene monomer, ABS resin, etc. χ, by reacting with acetic acid: vinyl acetate' can also be produced by Wacker reaction: aldehyde and its derivatives Ester and the like.

C 另和丙料適用於下述製造：例如，藉氨氧化而製造 =烯？ 選擇性氧化而製造之丙烯醛、丙烯酸及丙烯 -文二，猎側氧基反應而製造之正丁基醇、2_乙基己醇等之 側乳基醇，藉丙稀聚合而製造之聚丙稀，藉丙婦之選擇性 造之環氧丙燒及丙二醇等…可藉由瓦克反應 : 酮，進一步由丙酮製造曱基異丁基酮。由丙酮又可 製造丙酮氰醇’其最終被轉換為甲基丙烯酸甲酯。又 水合亦可製造異丙基醇。又，藉由將苯進行烧^ 之異丙苯作為原料，則可製造紛、雙紛a、聚碳酸 酉曰树脂。 另外，於上述一般之分離步驟之第3態樣及第4態樣中 :得之含有碳數2以下之烴與碳數3之烴的流體，較佳係 制、給至本製程以外之乙烯與丙烯之製造製程而進行精 衣、=為本製程以外之乙烯與丙稀之製造製程，可舉例如 制和乙燒等之蒸氣裂解製程。藉此，則可顯著削減本 製程的設備投資。 另方面，在無法將由本製程所生成之含乙烯之流體供 312ΧΡ/發明晒書(補件)/97·〇1/96ΐ35332 37 200831453 給至本製程以外之乙烯與丙烯之製造製程的情況下，則由 於需要於本製程中進行乙烯精製，故此時最好採用上述之 第1態樣或第2態樣。 {第3態樣中之分離步驟} [分離步驟] 〈氣體成分、液成分及水之分離：步驟（2C)、（3C)〉 本發明中，反應器出口氣體係進行冷卻，藉壓縮將冷卻 後之氣體流體（K)分離為氣體流體（L)、富含碳數4以上之 ί '烴並含有芳香族化合物的液流體（M)、及富含水之流體（步 驟（2C))，其後，將氣體流體（L)藉蒸餾等之一般分離步 驟，分離為富含碳數3以下之烴的流體與富含碳數4以上 之烴的流體（Ν)(步驟（3C))。 於步驟（2C)中，反應器出口氣體通常為300〜600°C左右 之溫度，而將此反應器出口氣體冷卻為20〜200°C左右。 此冷卻通常以熱交換器進行，但亦可藉由與較該氣體低溫 之流體混合而進行直接冷卻。經冷卻的流體（K)，係使用 1'壓縮機、液氣分離器0^11〇〇1^〇1^(11'11111)或油水分離器等， 藉壓縮分離為富含碳數6以下之烴的氣體流體（L)、富含 碳數4以上之烴並含有芳香族化合物的液流體（M)與富含 水的流體。又，上述熱交換器中，與反應器出口氣體進行 •熱交換的對象流體並無特別限定，較佳係供給至反應器之 •一種或複數之流體。 由此步驟（2C)所分離之富含碳數6以下之烴的氣體流 體（L)係含有烴，於步驟（3C)中，藉由蒸餾等之一般分離 312XP/發明說明書(補件)/97-01/96135332 38 200831453 步驟，分離為富含碳數3以下之烴的流體、與富含碳數4 以上之烴的流體（N)。 九 作為上述一般分離步驟之第丨態樣，可適用含有下述步 驟=方法：藉蒸餾分離為富含碳數2以下之烴的流體與$ 含碳數3以上之烴的流體，再將富含碳數3以上之烴的= 體，藉蒸顧分離為富含碳數3之烴的流體與富含碳數4以 上之烴的流體（Ν)。 作為上述一般分離步驟之第2態樣，可適用含有下述步 驟的方法·藉蒸饀为離為畐含碳數3以下之烴的流體盘富 含碳數4以上之烴的流體（Ν)，再將富含碳數3以下^二 的流體藉蒸餾分離為富含碳數2以下之烴的流體與富含 碳數3之烴的流體。 作為上述一般分離步驟之第3態樣，可適用含有下述步 驟的方法：藉蒸餾分離為富含碳數2以下之烴與碳數3之 烴的流體與富含碳數3以上之烴的流體，再將富含碳數3 j上之烴的流體藉蒸餾分離為富含碳數3之烴的流體與 富含碳數4以上之煙的流體（n)。 作為上述一般分離步驟之第4態樣，可適用含有下述步 驟的方法·藉蒸餾分離為富含碳數3以下之烴的流體與富 含妷數4以上之烴的流體（N)，再將富含碳數3以下之烴 的流體藉蒸餾分離為富含碳數2以下之烴與碳數3之烴的 流體與富含碳數3之烴的流體。 上述製程中，視需要較佳為進行淬火、鹼洗淨、脫水等 之處理。在於反應為出口氣體中含有含氧化合物的情況 312XP/發明說明書(補件)/97-01/96135332 39 200831453 由汗火步驟，可去除至少—部分之含氧化合物。在 :反應f出口氣體中含有二氧化碳等之酸性氣體的情況 • 猎鹼洗淨，可去除至少一部分之酸性氣體。 水之分離主要可藉由壓縮與冷卻進行凝縮。剩餘之水分 係以分子筛等之吸附劑進行去除。藉凝縮及/或吸附 而=除的水可供於活性污泥等之廢水處理步驟，亦可使用 於製程水。 在本發明之製程（以下有時稱為「本製程」）為接近茱氣 、裂解製程的情況下，自反應器出口氣體所回收的水較佳係 利用作為裂解之蒸氣源。x，亦可回收至本製程之反應器 中使用作為稀釋氣體。 〜 另外，自反應器出口氣體所得之碳數2以下的烴和碳數 3的L，更佳係藉由蒸德等之精製步驟所得之高純度乙稀 及丙烯。作為乙烯之純度，為95%以上、較佳99%以上。 更佳為99· 9%以上。作為丙烯之純度為95%以上、較佳99% 以上。更佳99. 9%以上。 ' 如此所得之乙烯及丙烯，可使用作為一般所製造之乙烯 及丙烯的所有衍生物，例如乙烯可使用於藉由氧化反應而 製造環氧乙烷、乙二醇、乙醇胺、二醇醚等，蕤由急 製造氯化乙稀基單體、⑴-三氯乙燒、氯化而 偏二氯乙烯，或藉由乙烯聚合而製造α稀烴、低密度或高 密度之聚乙烯，藉苯之乙基化而製造乙基笨等。 由乙烯所製造之乙二醇’可進一步將其作為原料而製造 聚對苯二曱酸乙二酯，將烯烴作為原料並藉由侧氧基反 312ΧΡ/發明說明書(補件)/97-01/96135332 40 200831453 應及^次之氫化反應而製造高級醇，將乙基苯作為原料而 製造笨乙烯單體、ABS樹脂等。又，藉由與醋酸之反應亦 可製造醋酸乙烯酯，藉由瓦克反應亦可製造乙醛及屬於其 之衍生物之醋酸乙酯等。 、^ 另外，丙烯可適用於下述製造：例如，藉氨氧化而製造 之丙烯腈，藉選擇性氧化而製造之丙烯醛、丙烯酸及丙烯 酸酯，藉侧氧基反應而製造之正丁基醇、2_乙基己醇等之 侧氧基醇’藉丙烯聚合而製造之聚丙烯，藉丙烯之選擇性 =而製造之環氧丙烧及丙二醇等。χ，可藉由瓦克反應 衣仏丙酮，進一步由丙酮製造甲基異丁基酮。由丙酮又可 製造丙酮氰醇，其最終被轉換為甲基丙烯酸甲酯。又，藉 由㈣水合亦可製造異丙基醇，藉由將苯進行燒基^C and propylene are suitable for the following manufacturing: for example, by ammoxidation to produce = ene? Acrolein, acrylic acid and propylene produced by selective oxidation, and a non-milk alcohol such as n-butyl alcohol or 2-ethylhexanol produced by reacting an oxo group, and polypropylene produced by polymerization of propylene Dilute, propylene glycol, propylene glycol, etc. can be made by the choice of a woman, and the ketone can be further produced from acetone by using a ketone reaction. Acetone cyanohydrin can be produced from acetone, which is ultimately converted to methyl methacrylate. Further hydration can also produce isopropyl alcohol. Further, by using cumene which is benzene-fired as a raw material, it is possible to produce a bismuth a, a polycarbonate resin. Further, in the third aspect and the fourth aspect of the above-mentioned general separation step, a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms is preferably produced and supplied to ethylene other than the process. The manufacturing process of the propylene manufacturing process, and the manufacturing process of ethylene and propylene other than the process of the propylene, for example, a steam cracking process such as production and baking. As a result, equipment investment in this process can be significantly reduced. On the other hand, in the case where the ethylene-containing fluid produced by the process cannot be supplied to the manufacturing process of ethylene and propylene other than the process of supplying 312 ΧΡ/inventive book (supplement)/97·〇1/96ΐ35332 37 200831453, Therefore, since it is necessary to carry out ethylene refining in the present process, it is preferable to use the first aspect or the second aspect described above. {Separation step in the third aspect} [Separation step] <Separation of gas component, liquid component and water: Steps (2C), (3C)> In the present invention, the reactor outlet gas system is cooled and cooled by compression. The latter gas fluid (K) is separated into a gas fluid (L), a liquid fluid (M) rich in carbon number 4 or more and containing an aromatic compound, and a water-rich fluid (step (2C)), Thereafter, the gas fluid (L) is separated into a fluid rich in carbon atoms of 3 or less and a fluid rich in hydrocarbons having 4 or more carbon atoms by a general separation step of distillation or the like (step (3C)). In the step (2C), the reactor outlet gas is usually at a temperature of about 300 to 600 ° C, and the reactor outlet gas is cooled to about 20 to 200 ° C. This cooling is usually carried out in a heat exchanger, but it can also be directly cooled by mixing with a fluid at a lower temperature than the gas. The cooled fluid (K) is separated into a carbon-rich number of 6 or less by compression using a 1' compressor, a liquid-gas separator 0^11〇〇1^〇1^(11'11111), or a water-oil separator. The hydrocarbon gas (L) of the hydrocarbon, the liquid fluid (M) rich in carbon atoms of 4 or more and containing the aromatic compound, and the water-rich fluid. Further, in the heat exchanger, the target fluid to be exchanged with the reactor outlet gas is not particularly limited, but is preferably one or a plurality of fluids supplied to the reactor. The gas fluid (L) having a hydrocarbon having a carbon number of 6 or less separated by the step (2C) contains a hydrocarbon, and in the step (3C), the general separation by distillation or the like 312XP / invention specification (supplement) / 97-01/96135332 38 200831453 The step is to separate a fluid having a carbon number of 3 or less and a fluid (N) having a hydrocarbon having a carbon number of 4 or more. Nine, as a second aspect of the above general separation step, may be applied to a process comprising the steps of: separating a fluid having a carbon number of 2 or less and a hydrocarbon having a carbon number of 3 or more by distillation, and then enriching A body containing a hydrocarbon having 3 or more carbon atoms is separated into a fluid having a carbon number of 3 and a fluid having a carbon number of 4 or more by distillation. As a second aspect of the above-described general separation step, a method comprising the following steps can be applied: a fluid disk having a hydrocarbon number of 4 or more carbon atoms which is a hydrocarbon disk having a hydrocarbon having a carbon number of 3 or less. Then, the fluid rich in carbon number 3 or less is separated by distillation into a fluid rich in hydrocarbons having a carbon number of 2 or less and a fluid rich in carbon 3 hydrocarbons. As a third aspect of the above general separation step, a method comprising the steps of separating a fluid having a carbon number of 2 or less and a hydrocarbon having a carbon number of 3 and a hydrocarbon having a carbon number of 3 or more by distillation may be applied. The fluid is further separated by distillation into a fluid rich in carbon number 3 hydrocarbons and a fluid rich in carbon number 4 or higher (n). As a fourth aspect of the above-described general separation step, a method comprising the steps of: separating a fluid having a hydrocarbon having a carbon number of 3 or less and a fluid having a hydrocarbon having a carbon number of 4 or more (N) by a method comprising the following steps; The fluid rich in hydrocarbons having a carbon number of 3 or less is separated by distillation into a fluid rich in carbon number 2 or less and a hydrocarbon having 3 carbon atoms and a fluid rich in carbon number 3 hydrocarbon. In the above process, it is preferred to carry out the treatment such as quenching, alkali washing, dehydration or the like as needed. In the case where the reaction is an oxygen-containing compound in the outlet gas 312XP/Invention Manual (Supplement)/97-01/96135332 39 200831453 By the sweat step, at least a part of the oxygen-containing compound can be removed. In the case where the reaction gas at the outlet of the reaction f contains an acid gas such as carbon dioxide. • The game is washed to remove at least a part of the acid gas. The separation of water can be mainly condensed by compression and cooling. The remaining water is removed by an adsorbent such as a molecular sieve. The water removed by condensation and/or adsorption can be used for wastewater treatment steps such as activated sludge, and can also be used for process water. In the case where the process of the present invention (hereinafter sometimes referred to as "the process") is close to the helium gas or cracking process, the water recovered from the reactor outlet gas is preferably used as a vapor source for cracking. x can also be recycled to the reactor of this process for use as a diluent gas. Further, the hydrocarbon having a carbon number of 2 or less and the L having a carbon number of 3 obtained from the gas at the outlet of the reactor are more preferably high-purity ethylene and propylene obtained by a purification step such as steaming. The purity of ethylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more. The purity of propylene is 95% or more, preferably 99% or more. More preferably 99.9% or more. 'Ethylene and propylene thus obtained can be used as all derivatives of ethylene and propylene which are generally produced, for example, ethylene can be used for producing ethylene oxide, ethylene glycol, ethanolamine, glycol ether, etc. by oxidation reaction.蕤 急 制造 蕤 蕤 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化 氯化Ethylation to produce ethyl stupid and the like. Ethylene glycol manufactured by ethylene can be further used as a raw material to produce polyethylene terephthalate, using olefin as a raw material and by side oxy group 312 ΧΡ / invention specification (supplement) / 97-01 /96135332 40 200831453 A higher alcohol is produced by a hydrogenation reaction, and a styrene monomer, an ABS resin, or the like is produced using ethylbenzene as a raw material. Further, vinyl acetate can be produced by a reaction with acetic acid, and acetaldehyde and an ethyl acetate derived therefrom can be produced by a WACKER reaction. Further, propylene can be suitably used in the production of, for example, acrylonitrile produced by ammoxidation, acrolein produced by selective oxidation, acrylic acid and acrylate, and n-butyl alcohol produced by a side oxy group reaction. A non-oxyl alcohol such as 2-ethylhexanol, a polypropylene produced by polymerization of propylene, a propylene-acrylic acid produced by the selectivity of propylene, and propylene glycol. Alternatively, methyl isobutyl ketone can be further produced from acetone by the WACKER reaction of acetone. Acetone cyanohydrin can be produced from acetone, which is ultimately converted to methyl methacrylate. Further, isopropyl alcohol can also be produced by (4) hydration, by burning benzene ^

而衣造之異丙苯作為原料，則可製造盼、雙紛AAnd the cumene made by clothing can be used as a raw material to create a hope and a double

酯樹脂。 A 另外，於上述分離步驟之第3態樣及第4態樣中所得之 =碳數2以下之烴與碳數3之烴的流體，較佳係供給至 卜之乙㈣丙社製造製程而進行精製。作為本 二^ :之乙烯與丙烯之製造製程，可舉例如石油腦和乙 =之減裂解製程。藉此，則可顯著削減本製程的設備 另-方面，在無法將由本製程所生成 給;本製程以外之乙稀與丙稀之製造製程的情兄下:1' 進行乙烯精製，故此時最好採用上述之 弟1悲樣或第2態樣。 312ΧΡ/發明說明書(補件)/97·01/96135332 41 200831453 {第1及第2態樣} &lt;石反數4以上之烴的分離及回收··步驟（3A)、（犯）〉 自反應器出口氣體所分離之富含碳數4以上之烴的流 體（A)(以下稱為碳數4以上之烴流體之至少一部 •分，係回收至反應器，剩餘的流體則自本製程取出。 於此，「自本製程取出」係指不回收至本製程之反應器， 可、、二由配g直接供給於其他製程，亦可經由配管暫時貯藏 於槽中再供給至其他製程。又，亦可未供應至其他製程而 1 使用作為燃料。 作為將碳數4以上之烴流體（A)回收至反應器之方法的 第1態樣，可適用含有下述步驟的方法；將碳數4以上之 ，流，（A)之-部分⑻自該製程取出，將剩餘的流體⑹ 藉由蒸餾等之一般分離手法分離為芳香族化合物濃产（重 量％)較流體⑹低之流體（D)與碳數4之煙濃度較流ς⑹ 低之流體（Ε)，並將流體（D)回收至反應器，將流體（Ε)自 該製程取出。 U作為第2態樣，可適用含有下述步驟的方法：將碳數4 以上之烴流體（Α)藉由蒸餾等之一般分離手法，分離為芳 香族化合物濃度較流體（Α)低之流體（G)與碳數4之烴濃 度較流體（A)低之流體（F)，將流體（F)之至少一部八^該 製程取出，並將流體（G)之至少一部分之流體（1):二至工 應器，將剩餘的流體（H)自該製程取出。 在使用含有碳數4以上之石蠟之原料作為碳數4以上之 稀烴原料的情況下，上述第！態樣中之流體⑻或第2態 312XP/發明說明書(補件)/97-01/96135332 42 200831453 故難由於屬於多量地含有石壞的組成流趙， 程:接:二二Γΐ分f行分離精製。因此，在該製 有效利用作'為裂nr’Μ係供給至蒸氣裂解製程， 藉此此等流體⑻、⑻可成為蒸氣裂解製程中之 和丙稀製造用原料。此時，較冷 之至少-部分盘氫化觸婵接冑“體⑻或流體⑻ 脚m/二 而將石蠟濃度較流體⑻ /-()更4增加之流體供給至蒸氣裂解製程巾。 煙濃度較高的流體供給至蒸氣裂解製程的裂解，則 於衣解内將容易發生碳析出，故不佳。 、 另外，此情況下，流體（B)或流體（H)中所含之芳 ^勿濃度的合計較佳為未滿5.〇體積％、更佳未滿3 〇、體 積公若芳香族化合物濃度較高，則於供給至 析出較多，且有乙烯產率降低的傾向，故不佳。解 尺 另外，上述第1態樣中之流體⑻或第2態樣中之 (JO,較佳係混合於蒸氣裂解製㈣之分解汽油顧分 藉此，可有效利用流體（E )或流體（f )。 於此所謂分解汽油，係指主要含有碳數5以上、ι〇以 下之石蟻、烯烴、二烯、芳香族化合物的流體，Ester resin. Further, the fluid of the hydrocarbon having a carbon number of 2 or less and the hydrocarbon having a carbon number of 3 obtained in the third aspect and the fourth aspect of the separation step is preferably supplied to the manufacturing process of the B. Refined. As a manufacturing process of ethylene and propylene, for example, a petroleum brain and a sulphur reduction process can be mentioned. In this way, the equipment of this process can be significantly reduced, and it is impossible to process the process produced by the process; the manufacturing process of the ethylene and propylene other than the process: 1' for ethylene refining, so at this time It is good to adopt the above-mentioned brother 1 sad or second. 312ΧΡ/Invention Manual (Supplement)/97·01/96135332 41 200831453 {First and Second Aspects} &lt;Separation and recovery of hydrocarbons with a stone number of 4 or more··Steps (3A), (offences) The fluid (A) having a carbon number of 4 or more hydrocarbons separated by the outlet gas of the reactor (hereinafter referred to as at least one part of the hydrocarbon fluid having a carbon number of 4 or more is recovered into the reactor, and the remaining fluid is derived from the present The process is taken out. Here, "taken out from the process" means a reactor that is not recycled to the process, and may be directly supplied to other processes by the g, or may be temporarily stored in the tank via a pipe and then supplied to other processes. Further, it may be used as a fuel without being supplied to another process. As a first aspect of the method of recovering a hydrocarbon fluid (A) having a carbon number of 4 or more to the reactor, a method comprising the following steps may be applied; The carbon number of 4 or more, the flow, and the part (8) of (A) are taken out from the process, and the remaining fluid (6) is separated into a fluid having a lower aromatic product (% by weight) than the fluid (6) by a general separation method such as distillation. (D) a fluid with a carbon number of 4 that is lower in concentration than the flowing (6), and The fluid (D) is recovered to the reactor, and the fluid (Ε) is taken out from the process. U As a second aspect, a method comprising the steps of: discharging a hydrocarbon fluid having a carbon number of 4 or more by distillation or the like can be applied. The general separation method is to separate a fluid (F) having a lower concentration of aromatic compounds than a fluid (Α) and a fluid having a lower hydrocarbon concentration of carbon 4 (A) than at least a fluid (A), and at least one portion of the fluid (F). The process is taken out, and at least a part of the fluid (1) of the fluid (G) is taken to the working device, and the remaining fluid (H) is taken out from the process. The raw material containing paraffin having a carbon number of 4 or more is used. In the case of a dilute hydrocarbon raw material having a carbon number of 4 or more, the fluid (8) or the second state 312XP/invention specification (supplement)/97-01/96135332 42 200831453 in the above-described first aspect is difficult because it contains a large amount of stone. The bad composition flow Zhao, Cheng: Connection: 22 minutes, f line separation and refining. Therefore, the system is effectively used as a 'cracking nr' system to supply to the steam cracking process, whereby these fluids (8), (8) can become The raw material for the production of propylene in the steam cracking process. At this time, the colder at least - part of the disk is hydrogenated. The fluid with a higher paraffin concentration than the fluid (8) /-() is supplied to the steam cracking process towel by contacting the body (8) or the fluid (8) foot m/2. The fluid having a higher smoke concentration is supplied to the cracking process of the steam cracking process. Further, in the case of the solution, carbon deposition is likely to occur, which is not preferable. Further, in this case, the total concentration of the aromatics contained in the fluid (B) or the fluid (H) is preferably less than 5. When the volume %, more preferably less than 3 〇, and the volume of the aromatic compound is high, the amount of the aromatic compound is relatively high, and the ethylene yield tends to decrease, which is not preferable. The first aspect is also obtained. In the fluid (8) or the second aspect (JO, preferably mixed with the vapor cracking system (4), the decomposition gasoline can be utilized to effectively utilize the fluid (E) or the fluid (f). The term "decomposition of gasoline" as used herein refers to a fluid mainly containing a carbon number of 5 or more, an olefin, a diene, or an aromatic compound.

自分解汽油回收有效成分。作為有效成分，可舉例 5之烴和苯、曱苯、二甲笨等之芳香族化合物。 A 若於分解汽油中含有碳數4之烴，則自分解汽油戶 之碳數5之烴流體中將混入碳數4之烴，故不佳。因此， 混合於分解汽油餾分中之流體（E )或流體（F )中之碳數4 312XP/發明說明書(補件)/97-01/96135332 43 200831453 之烴較佳為未滿5重量％。更佳為未滿2重量 ^為第1態樣之特徵，係由於可藉由取出流體⑻而減 &amp;洛館等之分離步驟的負擔’故於效益費用與設備投資費 用之兩方面上將較第2態樣更為有利。然而，流體⑻係 與流體（Α)相同組成的流體，相較於第2態樣所得之流體 (Η) ’芳香族化合物濃度變高。因此，需配合取 的用途而選定製程。 {第3態樣} t 〈碳數4以上之烴的回收··步驟（4c)&gt; 由步驟（3C)所分離之富含碳數4以上之炉 ⑻(以下稱為碳數4以上之烴流 ；本 製程取出，將剩餘的流體⑻回收至反應器，又刀二 驟令所凝縮之富含碳數4以上之烴的流體並含有芳香族 化合物的液流體（M)之至少一部分係自本製程中取出。、 於此自本衣私取出」係指不回收至本製程之反應器， 可經由配管直接供給於其他製程，亦可經由配管暫時貯藏 U於槽中再供給至其他製程。又，亦可未供應至其他製程而 使用作為燃料。 液流體（M)可藉蒸餾分離為芳香族化合物濃度（重量％) 較液流體（M)低之流體（R)與碳數4之烴濃度較液流體（m) 低之流體（s)。此時，較佳係將流體（R)送回至從流體、 (L)、（Ν)、（Ρ)及（Q)選出之任一或複數之流體的流通處。 於液流體（Μ)中含有多量碳數4以下之烴的情況下，較佳 係進行此蒸餾操作。 312ΧΡ/發明說明書(補件)/97-01/96135332 44 200831453 烯碳數4以上之石蠟之原料作為碳數4以上之 量地含有石纖的植成、、^ f )、（Ρ)、⑻由於屬於多 行分離梦制。^ 難以將丁稀等之有效成分進 佳係將在該製程為接近蒸氣裂解製程時’較 1!此4流體00、⑻、⑻之任-種以上之流體供认 ^裂解製程，有效利料為裂解原料。 猎此’可成為蒸氣裂解製程中之乙烯和 交佳係使流體(Μ)、 二將石蟻濃度較流體(Μ)，、(心 古曰加之机體供給至療氣裂解製程中。由於若將稀 咼的流體供給至基教解制0 又乂 發生碳析出，故不^ 的裂解’則於裂解内將容易 另外，此情況下’流體00、⑻、⑻中所 化合物濃度的合計較佳為未滿5 曰矢 „ Μ 土 υ骽槓％、更佳未滿3. 〇 石右夕 化合物濃度較高，則於供給至裂解時之 反析出較夕，且有乙烯產率降低的傾向，故不佳。 另外，上述流體（S)較佳係混合於菽氣裂 f 解;气油鶴分中。藉此，可有效利用流體 ⑷中之碳數4以下之烴濃度較低時，亦； 混合於分解汽油顧分中。 股W直接 於此，所謂分解汽油，係指主要含有碳數5以上、 以下之石壤、烯烴、二稀、芳香族化合物的流體，視 可自分解汽油回收有效成分。作為有效成分，可兴2 數5之烴和苯、甲苯、二甲笨等之芳香族化合物y碳 312XP/發明說明書(補件)/97-01/96135332 45 200831453 ?於分解汽油中含有碳數4之烴，則自分解汽油所回收 數5之烴流體中將混入碳數4之烴，故不佳。因此， 此:於分解汽油餾分中之流體（M)或流體（S)中之碳數4 之烴較佳為未滿5重量％。更佳為未滿2重量％。 〈反應器入口之基質濃度的控制〉 上述第1您樣中，藉由控制流體（B)及流體（E)之流量， ，可控制回收至反應器之流體（D)中所含之石蠟等之稀 氣體流量。 旦另外，於第2態樣中，藉由控制流體（F)及流體（η)之流 1，則可控制回收至反應器之流體（1)中所含之石 稀釋氣體流量。 上述第3態樣中，藉由控制流體（M)及流體（p)、或流體 (P)、流體（R)及流體（S)之流量，再者，藉由控制送回至 流體（K)、（L)、⑻、（P)及⑻所選出之任i種或2種以 上之流體流通處的流體（R)之流量和其送回處，則可控制 回，至反應器之流體(Q)所含之石i等之稀釋氣體流量。 藉此，較佳係將供給至反應器之總供給原料中的碳數4 以上之烯烴與曱醇與二甲基醚的合計濃度（基質濃度）控 制於20體積％以上、8〇體積％以下。 [與蒸氣裂解製程之統合] 於蒸氣裂解製程中，大多係將自所得之碳數4之烴流體 (BB餾分）經去除必要成分的低價值流體（主要為c4萃餘 液-2)進行氫化並送回至裂解器。 、 本製程中，可將此低價值流體作為原料，並可將本製程 312XP/發明說明書(補件)/97-01/96135332 46 200831453 中所不需要的流體於蒸氣裂解製程中進行利用，故由此觀 點而言，屬於可有效利用彼此為低價值之流體而效率極佳 的製程。 [製程之實施態樣] 以下，針對本發明製程之實施態樣，參照圖式而進行說 明〇 η 圖1表示本發明製程之第1態樣，圖2表示第2態樣。 圖卜2中，1〇為反應器，20為第1分離精製系統，30Α、 30Β為第2分離精製系統。1〇1〜114分別表示配管。 〈第1態樣（圖1)之說明〉 將碳數4以上之烯烴原料，來自第2分離精製系統30Α 之碳數4以上之烴流體（D)、曱醇及二曱基醚中之至少一 者’分別經由配管101、102、103及配管1〇4供給至反應 器10。於供給至反應器1〇之碳數4以上之烯烴原料中可 s有故數4以上之石纟敗類，例如正丁烧和異丁燒等。又， 經由配管104供給至反應器1〇之原料流體中，亦可含有 丁二烯和芳香族化合物。如上述般，原料流體中之丁一烯 濃度通常為2.0體積《/◦以下，芳香族化合物之合計量=相 對於配管104之原料流體中所含之碳數4以上之烯烴^合 計置，以莫耳比計通常為未滿0 05。又，原料流體 經由配管1〇卜102及1〇3所供給之流體的總計，作此^ 亚不需要一定要在置入反應器前進行合流， 八 地供給至反應器10。供給至反應器1〇之二=々二可分別 應器10内與觸媒進行接觸及反應，而到^人將於反 仔到含有丙烯、其 312XP/發明說明書(補件)/97-0196^5332 47 200831453 他烯烴、石蠟類、芳香族化合物及水的反應器出口氣體。 反應器出口氣體係由配管丨〇5而送給至冷卻、壓縮、蒸 顧等一般之分離精製系統2〇，由此分離精製系統2〇分離 為西含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（A)及萄含水的流體，並分別經由配管106、108、107 而取出。於此，富含碳數3以下之烴的流體係表示一種以 上之机體。例如，可為包括了所有碳數3以下之烴的一種 流體、，亦可為富含碳數2以下之烴的流體與富含碳數3之 烴的流體、和富含碳數2以下之烴與碳數3之烴的流體與 富含碳數3之烴的流體般之二種流體。再者，亦可為三種 以上之流體。 富含碳數4以上之烴的流體（A)之一部分係藉配管1〇9 而，出至製私外，剩餘之流體⑹係經由配管而供給 至蒸餾等之一般的分離精製系統3〇A中。 分的流體（b)亦可取出至勢程外,. 〇p 衣私外。此時，所取出之流體（B) 亦可利用作為蒸氣裂解製程㈣解原料。此情況下，較佳 使取出之流體⑻與氫化觸媒接觸而提高石壤濃度 Ϊ:體而供給至蒸氣裂解製程。此時之取出之流體⑻之 方香族化合物濃度的合計最好未$5Q體積％。 二中’分離為芳香族化合物濃度低於 應器10，流體(E)係藉由配管u :己：二02而：收至反 之流體⑻亦可混合於，心1製程取出。取出 “、、孔4解製程等之分解汽油餾分 312XP/發明說明書(補件)/97-01/96135332 48 200831453 中。此情況下，流體（E)所含之碳數4之烴的合計濃度較 佳為未滿5重量％。 流體（D)之一部分之流體（以下稱「流體（χ)」）可取出至 製程外。此時，取出之流體（Χ)亦可利用作為蒗 程之裂解原料。此情況下，㈣㈣為使取出、之流體⑴ 與虱化觸媒接觸而提高石蠟濃度的流體而供給至蒸氣裂 解製程。此時之取出之流體（X)之芳香族化合物濃&amp;的^ 計最好未滿5 · 0莫耳％。Self-decomposing gasoline to recover active ingredients. The active component may, for example, be a hydrocarbon of 5 or an aromatic compound such as benzene, toluene or dimethylbenzene. A If a hydrocarbon having a carbon number of 4 is contained in the decomposed gasoline, a hydrocarbon having a carbon number of 4 is mixed into the hydrocarbon fluid of the self-decomposing gasoline household, which is not preferable. Therefore, the hydrocarbons mixed in the fluid (E) or the fluid (F) in the decomposition gasoline fraction are preferably less than 5% by weight of the hydrocarbons of the carbon number 4 312 XP / invention specification (supplement) / 97-01/96135332 43 200831453. More preferably, the weight of the second aspect is the feature of the first aspect, because the burden of the separation step of the column can be reduced by taking out the fluid (8), so that both the benefit cost and the equipment investment cost are It is more advantageous than the second aspect. However, the fluid (8) has the same composition as the fluid (Α), and the concentration of the fluid (Η)' aromatic compound obtained in the second aspect becomes higher. Therefore, it is necessary to select a custom process for the purpose of taking it. {Third aspect} t <Recovery of hydrocarbon having 4 or more carbon atoms·Step (4c)&gt; The furnace (8) having a carbon number of 4 or more separated by the step (3C) (hereinafter referred to as a carbon number of 4 or more) a hydrocarbon stream; the process is taken out, the remaining fluid (8) is recovered to the reactor, and at least a portion of the liquid fluid (M) containing the hydrocarbon having a carbon number of 4 or more and containing the aromatic compound is condensed. It is taken out from the process. Here, the reactor is not recycled to the process. It can be directly supplied to other processes via piping. It can also temporarily store U in the tank and supply it to other processes via piping. Alternatively, it may be used as a fuel without being supplied to other processes. The liquid fluid (M) may be separated by distillation into an aromatic compound concentration (% by weight). The fluid (R) and the carbon number 4 are lower than the liquid fluid (M). a fluid (s) having a lower hydrocarbon concentration than the liquid fluid (m). At this time, it is preferred to return the fluid (R) to the fluid, (L), (Ν), (Ρ), and (Q). The flow of one or more fluids. In the case where the liquid fluid (Μ) contains a large amount of hydrocarbons having a carbon number of 4 or less, it is preferred This distillation operation is carried out. 312ΧΡ/Invention Manual (Supplement)/97-01/96135332 44 200831453 The raw material of paraffin having an olefin number of 4 or more is contained as a carbon fiber of 4 or more, and is f (Ρ), (8) Because it belongs to a multi-line separation dream system. ^ It is difficult to put the active ingredients such as Ding Ding into the Jiashi system. When the process is close to the steam cracking process, the fluids of the above-mentioned 4 fluids 00, (8), and (8) are supplied to the cracking process. The effective material is Crack the raw material. Hunting this can be used in the steam cracking process of ethylene and Jiaojia system to make the fluid (Μ), the concentration of the stone ants is more fluid (Μ), (the heart is added to the body to the gas cracking process. When the dilute fluid is supplied to the base solution and the carbon deposition occurs, the cracking of the mixture is easy to be carried out in the cracking. In this case, the total concentration of the compounds in the fluids 00, (8), and (8) is preferably Less than 5 曰 „ Μ υ骽 υ骽 % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % Further, the fluid (S) is preferably mixed in the gas cracking solution; the gas oil crane is used. Thereby, the hydrocarbon concentration in the fluid (4) having a carbon number of 4 or less can be effectively utilized; It is mixed with the decomposition of gasoline. The stock W is directly related to this. The so-called decomposition of gasoline refers to a fluid mainly containing rocky carbon, olefin, dilute or aromatic compound having a carbon number of 5 or more, which is effective as a self-decomposing gasoline. Ingredients. As an active ingredient, it can be used as a hydrocarbon and benzene and toluene. Aromatic compound y carbon 312XP/inventive manual (supplement)/97-01/96135332 45 200831453 ? In the decomposition of gasoline containing hydrocarbons of carbon number 4, the hydrocarbons recovered from the decomposed gasoline are 5 It is not preferable to mix a hydrocarbon having a carbon number of 4. Therefore, it is preferable that the hydrocarbon having a carbon number of 4 in the fluid (M) or the fluid (S) in the decomposition gasoline fraction is less than 5% by weight. More preferably Less than 2% by weight. <Control of the substrate concentration at the reactor inlet> In the first sample, by controlling the flow rates of the fluid (B) and the fluid (E), the fluid recovered to the reactor (D) can be controlled. The flow rate of the dilute gas such as paraffin contained in the reactor. In addition, in the second aspect, by controlling the flow 1 of the fluid (F) and the fluid (η), the fluid (1) recovered to the reactor can be controlled. The flow rate of the stone dilution gas contained in the third aspect, by controlling the flow rates of the fluid (M) and the fluid (p), or the fluid (P), the fluid (R), and the fluid (S), The flow rate of the fluid (R) that is returned to the fluid distribution of any one or more of the fluids selected by the fluids (K), (L), (8), (P), and (8) and At the back, it is possible to control the flow rate of the diluent gas to the stone (i) contained in the fluid (Q) of the reactor. Therefore, it is preferred to supply the olefin having 4 or more carbon atoms in the total feedstock supplied to the reactor. The total concentration (base concentration) with decyl alcohol and dimethyl ether is controlled to be 20% by volume or more and 8% by volume or less. [Integration with steam cracking process] In the steam cracking process, most of the carbon numbers are obtained from the carbon number obtained. The hydrocarbon fluid (BB fraction) of 4 is hydrogenated by a low-value fluid (mainly c4 raffinate-2) which removes the necessary components and sent back to the cracker. In this process, the low-value fluid can be used as a raw material, and The fluids not required in the process 312XP/invention specification (supplement)/97-01/96135332 46 200831453 can be utilized in the steam cracking process, so from this point of view, it is effective to utilize each other for low value. Fluid and efficient process. [Embodiment of Process] Hereinafter, an embodiment of the process of the present invention will be described with reference to the drawings. Fig. 1 shows a first aspect of the process of the present invention, and Fig. 2 shows a second aspect. In Fig. 2, 1〇 is a reactor, 20 is a first separation and purification system, and 30Α and 30Β are second separation and purification systems. 1〇1 to 114 respectively indicate piping. <Description of the first aspect (Fig. 1)> The olefin raw material having 4 or more carbon atoms, at least the hydrocarbon fluid (D) having a carbon number of 4 or more from the second separation and purification system 30, and at least one of a sterol and a decyl ether One of them is supplied to the reactor 10 through the pipes 101, 102, and 103 and the pipe 1〇4, respectively. The olefin raw material supplied to the reactor 1 having a carbon number of 4 or more may have a stone scum of 4 or more, for example, n-butyl sinter and isobutyl sinter. Further, the raw material fluid supplied to the reactor 1 via the pipe 104 may contain butadiene and an aromatic compound. As described above, the concentration of butadiene in the raw material fluid is usually 2.0 volume "/◦ or less, and the total amount of aromatic compounds = olefins of 4 or more carbon atoms contained in the raw material fluid of the pipe 104 is The molar ratio is usually less than 0 05. Further, the total amount of the fluid supplied from the raw material fluid through the pipes 1 and 102 and 1〇3 does not need to be merged before being placed in the reactor, and is supplied to the reactor 10 in eight places. Supply to the reactor 1 々 = 々 2 can be contacted and reacted with the catalyst in the reactor 10, and the person will be reversed to contain propylene, its 312XP / invention manual (supplement) / 97-0196 ^5332 47 200831453 He is the reactor outlet gas for olefins, paraffin, aromatics and water. The reactor outlet gas system is supplied to the general separation and purification system 2 such as cooling, compression, and distillation by the piping 丨〇5, whereby the separation and purification system 2 is separated into a fluid having a hydrocarbon having a carbon number of 3 or less in the west, and is rich. The fluid (A) containing hydrocarbons having a carbon number of 4 or more and the fluid containing water are taken out through the pipes 106, 108, and 107, respectively. Here, the flow system rich in hydrocarbons having a carbon number of 3 or less represents one or more bodies. For example, it may be a fluid including all hydrocarbons having a carbon number of 3 or less, a fluid having a carbon number of 2 or less and a fluid having a carbon number of 3, and a carbon number of 2 or less. The fluid of the hydrocarbon and the hydrocarbon of carbon number 3 is the same as the fluid of the hydrocarbon rich in carbon number 3. Furthermore, it is also possible to use three or more fluids. One part of the fluid (A) having a hydrocarbon having a carbon number of 4 or more is supplied to the private part by the piping 1〇9, and the remaining fluid (6) is supplied to a general separation and purification system such as distillation through a pipe. in. The sub-fluid (b) can also be taken out of the potential range. 〇p clothing is private. At this time, the taken out fluid (B) can also be used as a steam cracking process (4) to dissolve the raw materials. In this case, it is preferred that the taken-out fluid (8) is brought into contact with the hydrogenation catalyst to increase the rocky soil concentration and supply to the vapor cracking process. At this time, the total concentration of the aromatic compound of the fluid (8) taken out is preferably not less than $5Q% by volume. In the second middle, the concentration of the aromatic compound is lower than that of the reactor 10, and the fluid (E) is obtained by the piping u: hex: 02: the fluid (8) received in the opposite direction can be mixed, and the core 1 process is taken out. Take out the "Decomposed gasoline fraction 312XP / invention manual (supplement) / 97-01/96135332 48 200831453 of the ", hole 4 solution process, etc.. In this case, the total concentration of hydrocarbons of carbon number 4 contained in the fluid (E) Preferably, it is less than 5% by weight. A fluid (hereinafter referred to as "fluid") of one part of the fluid (D) can be taken out of the process. At this time, the taken-out fluid (Χ) can also be utilized as a cracking raw material for the process. In this case, (4) and (4) are supplied to the vapor cracking process in order to bring the fluid (1) taken out and contact with the bismuth catalyst to increase the fluid of the paraffin concentration. At this time, it is preferable that the concentration of the aromatic compound of the fluid (X) taken out is less than 5.0% by mole.

，上，流體（D)與流體（X)並不一定需要，但為了防止石蠟 類的蓄積，較佳係將至少一種流體自製程取出。 〈第2態樣（圖2)之說明〉 將石反數4以上之烯烴原料，來自第2分離精製系統 之碳數4以上之烴流體（1)、曱醇及二曱基醚中之至少一 者，分別經由配管101、1〇2、1〇3及配管1〇4供給至反應 器1〇。其後，於第i分離精製系統2〇中，由反應器1〇 之出口氣體，分離為富含碳數3以下之烴的流體、碳數4 以上之烴流體（A)及富含水的流體為止的步驟係與圖1相 同，故省略說明。 反數4以上之經流體（A )係藉配管1 〇 8而供給至蒸顧等 =一般的分離精製系統3〇β中。於分離精製系統30B中， 刀離為芳香族化合物濃度低於流體（A)的流體（G)與碳數4 ^上之烴濃度低於流體（A)的流體（F)。流體（F)係藉由配 二112而自該製程取出。取出之流體（F)亦可混合於蒸氣 衣解製程等之分解汽油餾分中。此情況下，流體（F)所含 画發明說明書(補件)_顧迎2 49 200831453 之碳數4之烴的合計濃度較佳為未滿5重量％。 流體（G)係藉配管113而 管自該製程：出:其之一部分⑻係經由配 ^ u 耘取出，剩餘之流體（I)係經由配管102 所取出之流體(H)亦可利用作為蒸氣 °此情況1r，較佳係作為使取出之流 $列λΛ冑媒接觸而提高石躐濃度的流體而供給至蒸 氟衣解製程。此時之取屮夕、六 、、 于之取出之机體（Η)之芳香族化合物濃度 Ο 的合计裒好未滿5. 〇體積％。 上述流體⑻之取出至製程外的步驟並不1需要，但 為了防止石蠛類的蓄積，較佳係將至少一種流體 自製程取出。 [製程之實施態樣] 〈第3實施態樣（圖3)&gt; 參照圖式而進行說 以下，針對本發明製程之實施態樣 明。 圖3表示本發明製程之一態樣。 圖3中，13為反應器，23為壓縮機，33為液氣分離器， 43為油水分離機，53為第j分離精製系統，63為第2分 離精製系統。3 01〜315分別表示配管。 將石反數4以上之烯煙原料，來自第1分離精製系統5 3 之石反數4以上之烴流體（Q)、曱醇及二曱基趟中之至少一 者，分別經由配管301、302 ' 303及配管304供給至反應 裔13。於供給至反應器13之碳數4以上之烯烴原料中可 含有碳數4以上之石蠟類，例如正丁烷和異丁烷等。又， 312ΧΡ/發明說明書(補件)/97-01/96135332 50 200831453 經由配管304供給至反應器13之原料流體中，亦可含有 丁二烯和芳香族化合物。如上述般，原料流體中之丁二烯 濃度通常為2.0體積％以下，芳香族化合物之合計量係相 對=配管304之原料流體中所含之碳數4以上之烯烴之合 計量，以莫耳比計通常為未滿〇〇5。又，原料流體係指 經由配管301、302及303所供給之流體的總計，但此等 並不萬要疋要在置入反應斋13前進行合流，亦可分別 地供給至反應器13。供給至反應器丨3之原料氣體將於反 應器13内與觸媒進行接觸及反應， 他稀經:石蝶類、芳香族化合物及水的：器有出丙口焊氣體其 反應益出口氣體係例如通過熱交換器而冷卻，冷卻後之 氣體流體（K)係藉由配管305而以壓縮機23進行升壓。壓 縮機23可為1個，但較佳為複數。於各壓縮機23後係設 置熱父換為及液氣分離器33，將壓縮後之氣體予以冷卻 後，分離為氣體流體（L)與凝縮成分。凝縮成分係經由配 管308而送給至油水分離機43並分離為富含碳數4以上 之烴的液流體（M)與富含水的流體，將富含水的流體由配 管310取出，富含碳數4以上之烴的液流體（μ)則由配管 309送給至第2分離精製系統63。 以液氣分離器3 3所分離之流體（l )係經由配管3 〇 7送給 至蒸餾等一般之第1分離精製系統53，並分離為富含碳 數3以下之烴的流體、富含碳數4以上之烴的流體（N)， 並分別經由配管313、314而取出。於此，富含碳數3以 下之煙的流體係表示一種以上之流體。例如，可為包括了 312XP/發明說明書(補件)/97·01/96135332 200831453 所有碳數3以下之煙的一種流體，亦 之烴的流體與富含石卢| ς + p 田3厌数Ζ ^严 之烴與石户數J，:反數3之煙的流體、和富含碳數2以下 種法體人再纟，呈的流體與富含碳數3之烴的流體般之二 種：：：再者，亦可為三種以上之流體。 315 J自1制1以上之煙的流體(Ν)之一部分(Ρ)係藉配管 ==?3取出:剩餘之流嶋經由配… 裂解:二兄Γ二Γ利用作為蒸氣裂解製程的 化觸媒接觸而担1 較佳係作為使取出之流體（ρ)與氫 程。此π之取屮回石峨濃度的流體而供給至蒸氣裂解製 好夫η出之流體（Ρ)之芳香族化合物濃度的合計最 好未滿5· 0體積％。 τ取 碳=二:油所分離之液流精係富含 接ώ， 含有芳香族化合物的液成分，其可直 =::,:時此产液流_則亦可利用作為蒸氣 啁句权冋石/辰度的流體而供給至蒸 ^ ^衣耘。此日守之取出之流體（M)之芳香族 声、 的合計最好未滿5.〇體積％。 物辰度 另外，在液流體(M)中之碳數4之烴濃度較低的情況 + ’亦n合至蒸氣裂解製程等之分解汽油m ^量Γ體（M)中所含之碳數4之烴的合計濃度最好未滿5 j外’液流體（M)之至少-部分較佳係於蒸顧等之 ~離步驟的第2分離精製系、统6G’分離為芳香族化合: 312： XP/發明說明書(補件)/97-01/96135332 52 200831453 濃度低於液流體（Μ)之流體（R)與碳數4之烴濃度低於液 流體（M)之流體（S)。於此，所分離之流體由配管lu 取出，但流體（R)最好送回至流體（κ)、流體（L)、流體（N)、 流體（P)、流體（Q)所流通之配管3〇5、3〇7、314、315、 302中之一處或複數處。 另一方面，流體（S)係由配管312取出，此流體（s)亦可 混合於蒸氣裂解製程等之分解汽油餾分中。此情況下，流 體（S)所含之碳數4之烴的合計濃度較佳為未滿5重量％。 、上述流體（P)之取出至製程外的步驟並不一定需要，但 為了防止石蠟類的蓄積，較佳係將至少一種流體的一部分 自製程取出。 〈實施例〉 以下列舉實施例而更具體地說明本發明，但本發明並不 限定於以下實施例。 [觸媒調製] 以下實施例、比較例所使用之觸媒，係如下述般所調製。 〈觸媒調製例〉 w依序將溴化四正丙基銨（TPABr)26 6g及氫氧化鈉4.8g &gt;谷，於水280g中，其次，緩慢加入膠體二氧化矽（Si〇2=：4〇 重里％，A1 &lt; 〇· 1重量％)75g與水35g的混合液，充分攪拌 ，得到水性凝膠。其次，將此凝膠填裝至1〇〇〇ml之高壓 釜中，於自壓下，一邊以300rpm進行攪拌、一邊以17〇 C進仃熱液合成72小時。生成物係藉加壓過濾而分離出 固體成分，予以充分水洗後以1〇〇〇c乾燥24小時。乾燥 312XP/發明說明書(補件)/97-01/96135332 53 200831453 後之觸媒係於空氣流通下以55(rc進行燒成6小時，得到The fluid (D) and the fluid (X) are not necessarily required, but in order to prevent the accumulation of paraffin, it is preferred to take out at least one fluid. <Description of the second aspect (Fig. 2)> The olefin raw material having a stone number of 4 or more, at least the hydrocarbon fluid (1) having a carbon number of 4 or more from the second separation and purification system, at least one of a sterol and a decyl ether One is supplied to the reactor 1 through the pipes 101, 1〇2, 1〇3, and the pipes 1〇4, respectively. Thereafter, in the i-th separation and purification system 2, the outlet gas of the reactor 1 is separated into a fluid rich in carbon atoms of 3 or less, a hydrocarbon fluid having 4 or more carbon atoms (A), and water-rich The steps up to the fluid are the same as those in Fig. 1, and therefore the description thereof will be omitted. The fluid (A) having a reverse number of 4 or more is supplied to the steaming or the like by the piping 1 〇 8 in a general separation and purification system 3 〇β. In the separation and purification system 30B, the knife is separated from the fluid (G) having a lower aromatic compound concentration than the fluid (A) and the fluid having a lower hydrocarbon concentration of 4% than the fluid (F). Fluid (F) is withdrawn from the process by dispensing 112. The taken-out fluid (F) may also be mixed in a decomposition gasoline fraction such as a vapor coating process. In this case, the total concentration of the hydrocarbons having a carbon number of 4 in the fluid (F) is preferably less than 5% by weight. The fluid (G) is taken from the process by the pipe 113. One of the parts (8) is taken out through the distribution, and the remaining fluid (I) is taken out from the pipe 102 (H). In this case, 1r is preferably supplied as a fluid for increasing the concentration of the sarcophagus by contacting the taken-out stream $ λ Λ胄 medium, and supplying it to the fluorination coating process. At this time, the total concentration of the aromatic compound (Ο) of the body (Η) taken out from the eve, the sixth, and the 裒 is less than 5. 〇 vol%. The step of taking out the fluid (8) out of the process is not required, but in order to prevent the accumulation of the sarcophagus, it is preferred to take out at least one of the fluids. [Embodiment of Process] <Third embodiment (Fig. 3)&gt; Referring to the drawings, the following is a description of the embodiment of the process of the present invention. Figure 3 shows an aspect of the process of the present invention. In Fig. 3, 13 is a reactor, 23 is a compressor, 33 is a liquid-gas separator, 43 is a water-oil separator, 53 is a j-th separation purification system, and 63 is a second separation purification system. 3 01 to 315 indicate piping, respectively. The olefinic material having a reciprocal number of 4 or more, at least one of a hydrocarbon fluid (Q), a sterol, and a diterpene hydrazine having a reverse number of 4 or more from the first separation and purification system 5 3 is respectively passed through the pipe 301, 302 '303 and piping 304 are supplied to the reaction descent 13. The olefin raw material having a carbon number of 4 or more supplied to the reactor 13 may contain paraffin wax having a carbon number of 4 or more, such as n-butane and isobutane. Further, 312 ΧΡ / invention specification (supplement) / 97-01/96135332 50 200831453 The raw material fluid supplied to the reactor 13 via the pipe 304 may contain butadiene and an aromatic compound. As described above, the concentration of butadiene in the raw material fluid is usually 2.0% by volume or less, and the total amount of the aromatic compounds is equivalent to the total amount of olefins having 4 or more carbon atoms contained in the raw material fluid of the pipe 304. The ratio is usually less than 〇〇5. Further, the raw material flow system refers to the total amount of the fluid supplied through the pipes 301, 302, and 303. However, it is not necessary to carry out the joining before the reaction 13 is placed, and it may be separately supplied to the reactor 13. The raw material gas supplied to the reactor 丨3 will contact and react with the catalyst in the reactor 13, and the sulphur: stone butterfly, aromatic compound and water: the device has a hydrogen welding gas, and the reaction is beneficial to the outlet gas. For example, it is cooled by a heat exchanger, and the cooled gas fluid (K) is pressurized by the compressor 23 by the pipe 305. The compressor 23 may be one, but is preferably plural. After the compressor 23, the hot father is replaced with a liquid gas separator 33, and the compressed gas is cooled, and then separated into a gas fluid (L) and a condensed component. The condensed component is supplied to the oil-water separator 43 via the pipe 308, and is separated into a liquid fluid (M) rich in carbon atoms of 4 or more and a water-rich fluid, and the water-rich fluid is taken out from the pipe 310. The liquid fluid (μ) containing a hydrocarbon having 4 or more carbon atoms is supplied to the second separation and purification system 63 from the pipe 309. The fluid (1) separated by the liquid-gas separator 3 is supplied to a general first separation and purification system 53 such as distillation via a pipe 3〇7, and is separated into a fluid rich in hydrocarbons having a carbon number of 3 or less, and is rich in The fluid (N) having a hydrocarbon having 4 or more carbon atoms is taken out through the pipes 313 and 314, respectively. Here, a flow system rich in carbon below 3 carbon atoms represents more than one fluid. For example, it may be a fluid including a 312XP/invention specification (supplement)/97·01/96135332 200831453 with a carbon number of 3 or less, and also a fluid of a hydrocarbon and a sulphate-rich | ς + p field 3 Ζ ^ Strict hydrocarbons and Shihu number J, the fluid of the inverse 3 smoke, and the carbon-rich number 2 or less, the fluid is the same as the fluid rich in carbon 3 Species::: In addition, there may be more than three fluids. 315 J. One part of the fluid (Ν) from the 1st and 1st cigarettes is taken by the piping ==?3. The remaining flow is passed through the... Cracking: The second brother and the second are used as the chemical touch of the steam cracking process. The medium contact is preferably used as the fluid (ρ) and the hydrogen path to be taken out. The total concentration of the aromatic compound in the fluid (Ρ) to be supplied to the steam cracking liquid is preferably less than 5% by volume. τ Take carbon = two: the oil is separated from the liquid stream, which is rich in tantalum, containing a liquid component of an aromatic compound, which can be directly =::,: when the liquid stream _ can also be used as a vapor 啁The rock of the vermiculite/Chendus is supplied to the steaming bowl. The total of the aromatic sounds of the fluid (M) taken out of this day is preferably less than 5% by volume. In addition, when the hydrocarbon concentration of the carbon number 4 in the liquid fluid (M) is low + 'the number of carbons contained in the decomposition gas of the vapor decomposition process, etc. The total concentration of the hydrocarbons of 4 is preferably less than 5 j. The at least part of the liquid fluid (M) is preferably in the form of steaming, etc. - the second separation and purification system from the step, the 6G' is separated into an aromatic compound: 312: XP/Invention Manual (Supplement)/97-01/96135332 52 200831453 Fluid (R) with a lower concentration than the liquid fluid (Μ) and a hydrocarbon with a carbon number of 4 is lower than the fluid of the liquid fluid (M) (S) . Here, the separated fluid is taken out by the pipe lu, but the fluid (R) is preferably sent back to the piping through which the fluid (κ), the fluid (L), the fluid (N), the fluid (P), and the fluid (Q) are circulated. One of 3〇5, 3〇7, 314, 315, 302 or plural. On the other hand, the fluid (S) is taken out by the pipe 312, and the fluid (s) may be mixed in the decomposition gasoline fraction such as a steam cracking process. In this case, the total concentration of the hydrocarbons having a carbon number of 4 contained in the fluid (S) is preferably less than 5% by weight. The step of taking out the fluid (P) out of the process is not necessarily required, but in order to prevent the accumulation of paraffin, it is preferred to take out a part of the at least one fluid. <Examples> Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. [Catalyst Modulation] The catalysts used in the following examples and comparative examples were prepared as follows. <Catalyst preparation example> w sequentially pulverized tetra-n-propylammonium (TPABr) 26 6g and sodium hydroxide 4.8g &gt; valley, in water 280g, and secondly, slowly added colloidal cerium oxide (Si〇2= : 4% by weight, A1 &lt; 〇·1% by weight) A mixture of 75 g and 35 g of water was thoroughly stirred to obtain an aqueous gel. Next, the gel was placed in a 1 〇〇〇ml autoclave, and while stirring at 300 rpm under self-pressure, it was hydrothermally synthesized at 17 〇C for 72 hours. The resultant was separated into a solid component by pressure filtration, washed thoroughly, and dried at 1 ° C for 24 hours. Drying 312XP/Invention Manual (Supplement)/97-01/96135332 53 200831453 The catalyst is fired at 55 (rc for 6 hours) under air circulation.

Na型之鋁矽酸鹽。 將此Na型之鋁矽酸鹽2〇g懸濁於1M之硝酸銨水溶液 偏中，於8(TC下攪拌2小時。處理後之液體藉由吸引 過滤分離出固體成分’予以充分水洗後，再度懸濁於1M 之硝酸銨水溶液40ml中，於8(rc下攪拌2小時。處理後 之液體藉由吸引過滤分離出固體成分，予以充分水洗後， ^以loot：乾燥24小時。乾燥後之觸媒係於空氣流通下以 1 ' 500 C進行燒成4小時，得到Η型之鋁矽酸鹽。 此觸媒藉XRD(X射線繞射）確認其沸石構造為MFI型。 將觸媒組成藉化學分析進行定量，結果為 Si〇2/Al2〇3=ll〇〇(莫耳比）。 [丙烯之製造] 以下表示使用了上述觸媒之丙烯的製造實施例及比較 例。 〈實施例1&gt; ' 使用上述觸媒進行丙烯之製造。 於反應使用常壓固定床流通反應裝置，於内徑6mm之石 英製反應管中，填充上述觸媒〇· 1〇g、石英砂1. 〇g之混 合物。於此反應器中，通過蒸發器供給作為相當於本發明 ’反應器入口氣體（圖1或圖2之配管104)組成之模擬氣體 -而調製成異丁烯（40體積％)、曱醇（20體積％)、苯（〇· 8體 積％)、丁二烯（0· 1體積％)及異丁烷（39. 1體積。/。）的氣體。 將反應溫度（反應器入口氣體溫度）設為550。〇。反應開始 312XP/發明說明書(補件)/97-01/96135332 54 200831453 70分鐘後，以氣相層析法進行生成物之分析。將此時之 反應條件及反應結果示於表1。 丙烯之選擇率為54.8% ,屬於非常高之程度。 進一步繼續反應，將曱醇之轉化率低於99%為止的時間 •作為觸媒壽命而進行評價。結果係觸媒壽命為312小時。 〈實施例2&gt; 除了將供給至反應器之苯濃度設為丨· 6體積％，將異丁 、烷濃度設為38· 3體積％以外，其餘依與實施例1相同之方 (法進行反應。反應開始7〇分鐘後，以氣相層析法進行生 成物之分析。將此時之反應條件及反應結果示於表1。 丙烯之選擇率為54· 4%，屬於非常高之程度。 進一步繼續反應，將曱醇之轉化率低於99%為止的時間 作為觸媒壽命而進行評價。結果係觸媒壽命為305小時。 〈比較例1 &gt; 除了將供給至反應器之苯濃度設為3.2體積％，將異丁 I燒濃度設為36· 7體積％以外，其餘依與實施例1相同之方 &gt;法進行反應。反應開始70分鐘後，以氣相層析法進行生 成物之分析。將此時之反應條件及反應結果示於表1。 丙烯之選擇率為51· 4%，相較於實施例1及2屬於非常 低之程度。 ’ 此係因為原料丁烯及/或曱醇與苯進行反應，生成了烧 • 基化苯，因為原本應使用於丙烯生成的丁烯及/或甲醇被 無用地浪費掉所致。 進一步繼續反應，將曱醇之轉化率低於99%為止的時間 312XP/發明說明書(補件)/97-01/96135332 55 ZUU5J14^3 作為觸媒壽命而進行評價。 相較於實施例1及2灸北# σ ’、尋媒壽命為221小時， 化苯堵塞了觸媒細孔=結果。推定此係因為烧基 十匕並促進積碳所致。 ^此，依照本發明方法，藉由使料族 部分不回收並取出，而#应雍哭 物之至夕 印而使反應盗入口之芳香族化合物濃度 条低，此丨月況將對達成高丙烯產率及抑制觸媒積碳劣 常有效果。 'Na type aluminum citrate. The Na-type aluminosilicate 2 〇g was suspended in a 1 M ammonium nitrate aqueous solution, and stirred at 8 (TC for 2 hours. The treated liquid was separated by solid filtration by suction filtration) and then thoroughly washed with water. The suspension was again suspended in 40 ml of a 1 M aqueous ammonium nitrate solution, and stirred at 8 (rc) for 2 hours. The treated liquid was separated by suction filtration to separate the solid component, and after sufficiently washing with water, it was dried by loot for 24 hours. The catalyst was fired at 1 '500 C for 4 hours under air flow to obtain a bismuth aluminate. This catalyst was confirmed by XRD (X-ray diffraction) to have a zeolite structure of MFI type. Quantitative analysis by chemical analysis revealed that Si 〇 2 / Al 2 〇 3 = ll 莫 (mol ratio). [Production of propylene] Hereinafter, production examples and comparative examples of propylene using the above catalyst are shown. 1&gt; 'The production of propylene was carried out using the above-mentioned catalyst. In the reaction, a normal-pressure fixed-bed flow reactor was used, and the above-mentioned catalyst 〇·1〇g, quartz sand was filled in a quartz reaction tube having an inner diameter of 6 mm. a mixture of this reactor, supplied by an evaporator It is prepared into isobutylene (40% by volume), decyl alcohol (20% by volume), benzene (〇·8 vol%) in the present invention as a simulated gas composed of the reactor inlet gas (the piping 104 of Fig. 1 or Fig. 2). a gas of butadiene (0.1% by volume) and isobutane (39.1% by volume). The reaction temperature (reactor inlet gas temperature) was set to 550. 反应 The reaction started 312XP/invention specification ( Supplement) /97-01/96135332 54 200831453 After 70 minutes, the product was analyzed by gas chromatography. The reaction conditions and reaction results at this time are shown in Table 1. The selectivity of propylene was 54.8%, belonging to Further, the reaction was further continued, and the time until the conversion of sterol was less than 99% was evaluated as the catalyst life. As a result, the catalyst life was 312 hours. <Example 2> In addition to the supply to the reaction The benzene concentration of the apparatus was set to 丨·6 vol%, and the isobutane and the alkane concentration were set to 38·3 vol%, and the same reaction as in Example 1 was carried out (the reaction was carried out by the method. After the reaction started for 7 minutes, the gas was used. Analysis of the product by phase chromatography. The reaction conditions at this time and The results are shown in Table 1. The selectivity of propylene was 54. 4%, which was a very high degree. Further, the reaction was continued, and the time until the conversion of sterol was less than 99% was evaluated as the catalyst life. The catalyst life was 305 hours. <Comparative Example 1 &gt; The same as Example 1 except that the concentration of benzene supplied to the reactor was 3.2% by volume, and the concentration of Isobutyl I was 36.7 % by volume. The reaction was carried out in the same manner as in the above method. After the reaction was started for 70 minutes, the product was analyzed by gas chromatography. The reaction conditions and the reaction results at this time are shown in Table 1. The selectivity of propylene was 51. 4%, which was a very low level compared to Examples 1 and 2. This is because the raw material butene and/or decyl alcohol reacts with benzene to form a burnt benzene because the butene and/or methanol originally used for propylene generation is wasted wastefully. Further, the reaction was continued, and the time until the conversion of sterol was less than 99% was evaluated by the 312 XP/invention specification (supplement)/97-01/96135332 55 ZUU5J14^3 as the catalyst life. Compared with Examples 1 and 2, Moxibustion # σ ', the media life was 221 hours, and the benzene blocked the catalyst pores = the result. It is presumed that this is due to the burning of the tenth and the promotion of carbon deposition. ^In this way, according to the method of the present invention, by making the material group portion not recovered and taken out, the amount of the aromatic compound concentration of the reaction thief is low, and the monthly concentration of the reaction is low. Propylene yield and inhibition of catalyst carbon deposition are often effective. '

312XP/發明說明書(補件)/97-01/96135332 56 200831453 [表1] 實施例1 實施例2 比較例1 反 應 條 件 丁烯濃度（體積°/〇) 40.0 40.0 40.0 甲醇濃度（體積%) 20.0 20.0 20.0 苯濃度（體積％) 0.8 1.6 3.2 丁二烯濃度（體積%) 0.1 0.1 0.1 丁烷濃度（體積％) 39.1 38.3 36.7 苯/丁嫦比（mol/mol) 0. 02 0. 04 0. 08 空間速度（Hi&quot;1) 4.6 4.6 4.6 反應溫度（°C) 550 550 550 反 應 結 果 甲醇轉化率（％) 100 100 100 丁烯轉化率（％) 64.8 64.9 65.5 丙烯選擇率（％) 54.8 54.4 51.4 乙烯選擇率（％) 15.1 14.9 13.8 C5+烯烴選擇率（％)※l 22.3 22.1 20.6 芳香族+石蠟選擇率（％)※2 7.8 8.6 14.2 觸媒壽命（Hr) 312 305 221 ※1 :碳數5以上之烯烴的選擇率 ※2:芳香族化合物與石蠟之合計的選擇率312XP/Invention Manual (Supplement)/97-01/96135332 56 200831453 [Table 1] Example 1 Example 2 Comparative Example 1 Reaction conditions Butene concentration (volume °/〇) 40.0 40.0 40.0 Methanol concentration (% by volume) 20.0 20.0 20.0 Benzene concentration (% by volume) 0.8 1.6 3.2 Butadiene concentration (% by volume) 0.1 0.1 0.1 Butane concentration (% by volume) 39.1 38.3 36.7 Benzene/butane ratio (mol/mol) 0. 02 0. 04 0. 08 Space velocity (Hi&quot;1) 4.6 4.6 4.6 Reaction temperature (°C) 550 550 550 Reaction result Methanol conversion rate (%) 100 100 100 Butene conversion rate (%) 64.8 64.9 65.5 Propylene selectivity (%) 54.8 54.4 51.4 Ethylene selectivity (%) 15.1 14.9 13.8 C5+ olefin selectivity (%)*l 22.3 22.1 20.6 Aromatic + paraffin selectivity (%)*2 7.8 8.6 14.2 Catalyst lifetime (Hr) 312 305 221 *1: Carbon number 5 The selectivity of the above olefins ※2: the selection ratio of the total of aromatic compounds and paraffin

57 312XP/發明說明書(補件)/97-01/96135332 200831453 以上雖參照特定實施態樣詳細地說明本發明，但在未脱 離本發明精神與範圍之下，本領域從業者當知可進行各種 變更和修正。 本申請案係根據2006年9月21日申請之日本專利申請 (特願2006-255503)、2006年9月21日申請之日本專利 申請（特願2006-255504)者，其内容係納入於此作為參照。 (產業上之可利用性） 本發明可提供一種用於使碳數4以上之烯烴、與曱醇及 一甲基醚中之至少一者進行反應而製造丙烯的新穎且經 濟之製程，以及統合了本製程與蒸氣裂解的新穎且經濟之 製程。 【圖式簡單說明】 圖1為表示本發明之丙烯之製造方法之實施形態之一 例的系統圖。57 312XP/Invention Manual (Supplement)/97-01/96135332 200831453 The present invention has been described in detail above with reference to the specific embodiments thereof, but without departing from the spirit and scope of the invention, Various changes and corrections. The application is based on the Japanese Patent Application (Japanese Patent Application No. 2006-255503) filed on Sep. 21, 2006, and the As a reference. (Industrial Applicability) The present invention can provide a novel and economical process for producing propylene by reacting at least one of a olefin having 4 or more carbon atoms with decyl alcohol and monomethyl ether, and integrating A novel and economical process for this process and steam cracking. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a system diagram showing an example of an embodiment of a method for producing propylene according to the present invention.

圖2為表示本發明之丙烯之製造方法之實施形態之其 他例的系統圖。 圖3為表示本發明之丙烯之製造方法之實施形態之其 他例的系統圖。 【主要元件符號說明】 1〇 ^ 13 反應器 20、53 23 30A 、 30B 、 63 33 第1分離精製系統 壓縮機 第2分離精製系統 液氣分離器 312XP/發明說明書(補件)/97-01/96135332 58 200831453 43 101〜114 、 30卜315 油水分離機 配管Fig. 2 is a system diagram showing another example of the embodiment of the method for producing propylene according to the present invention. Fig. 3 is a system diagram showing another example of the embodiment of the method for producing propylene according to the present invention. [Main component symbol description] 1〇^ 13 Reactor 20, 53 23 30A, 30B, 63 33 1st separation and purification system compressor 2nd separation and purification system liquid-gas separator 312XP / invention manual (supplement) / 97-01 /96135332 58 200831453 43 101~114, 30 Bu 315 oil water separator piping

Ο 312XP/發明說明書(補件)/97-01/96135332 59Ο 312XP/Invention Manual (supplement)/97-01/96135332 59

Claims (1)

200831453 十、申請專利範圍： 1. 一種丙稀之製造方法，係將含有碳數 與曱醇及二曱基醚中之至小 土 t 丄&lt;肺/工 H甲之至J 一者的原料，於觸媒存在下， 在反應器中接觸而製造丙烯者；其特徵為， 將該反應器出口流出翕辦r 爪®孔體（反應器出口氣體）中所含之 方香族化合物之至少一部分取出，並且， 山將該反應II出口流出氣體（反應器出口氣體）中所含之 =4以上之烯烴的至少__部分，於該反應㈣再次 媒接觸。 2. 如申請專利範圍第i項之丙烯之製造方法，其中，上 述碳數4以上之烯烴原料係含有碳數4以上之石蠟類。 3. 如申叫專利範圍第2項之丙烯之製造方法，其中上 述石蠟類係含有正丁烷及異丁烷中之至少一者。 4. 如申請專利範圍第4 3項中任一項之丙烯之製造方 法’其中，於上述供給至反應器之原料中含有丁二稀。 (,、5.如中請專利範圍第項中任—項之丙烯之製造方 法，其中，於上述供給至反應器之總原料中所含之芳香族 化合物的合計量，相對於該總原料所含之碳數4以上之烯 煙的合計量’以莫耳比計為未滿〇 〇5。 6. 如申請專利範圍第丨至5項中任一項之丙烯之製造方 法，其中，上述供給至反應器之碳數4以上之烯烴的量， 相對於該供給至反應器之甲醇莫耳數與二甲基醚莫耳數 之2倍的合計，以莫耳比計為〇·2以上且1〇以下。 7. 如申請專利範圍第1至6項中任一項之丙烯之製造方 312ΧΡ/發明說明書(補件)/97_〇1/96135332 60 200831453 法’其中’將上述供給至反應器之總原料中所含的碳數4 以上之稀烴與甲醇與二曱基趟的合計濃度（基質濃度），控 制於20體積％以上且8〇體積％以下。 8. 一種丙稀之製造方法’係將含有礙數4以上之稀烴、 與甲醇及二曱基醚中之至少一者的原料，於觸媒存在下， 在反應器中接觸而製造丙烯者；其特徵為包括含有以下步 驟（1)、（2)及（3A)之製程； (步驟（1):將碳數4以上之烯烴原料、自步驟（3A)所回 收之烴流體（D)、暨甲醇及二甲基醚中之至少一者，供給 至反應器，依反應器出口之碳數4以上之烯烴之莫耳流量 相對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與上述觸媒接觸，而自反應器出口得到 含有丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體 (反應器出口氣體）之步驟； 步驟（2) ··將來自上述步驟（1)之反應器出口氣體，分離 y為富含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（A)、及富含水之流體之步驟； 步驟（3A) ··將上述步驟（2)中之流體（A)之至少一部分的 流體（C) ’分離為芳香族化合物濃度較該流體（c)低之流體 • (D)、與碳數4之烴濃度較該流體（C)低之流體（E)，將上 述流體（D)回收至反應器，將上述流體（E)自該製程取出之 步驟。 9· 一種丙烯之製造方法，係將含有碳數4以上之烯烴、 與甲醇及二曱基醚中之至少一者的原料，於觸媒存在下， 312XP/發明說明書(補件)/97-01/96135332 61 200831453 在反應器中接觸而製造丙烯者；其特徵為包括含有以下步 驟（1)、（2)及（3A)之製程； 夕 步驟（1):將碳數4以上之烯烴原料、自步驟（3A)所回 收之烴流體（D)、暨曱醇及二曱基醚中之至少一者，供給 至反應裔’依反應裔出口之奴數4以上之烯煙之莫耳流量 相對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與上述觸媒接觸，而自反應器出口得到 厂含有丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體 (反應器出口氣體）之步驟； 步驟（2):將來自上述步驟（！）之反應器出口氣體，分離 為富含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（A)、及富含水之流體之步驟； 步驟（3A) ··將上述步驟（2)中之流體（A)之一部分（]8)從 该製程取出’將剩餘的流體（c)分離為芳香族化合物濃度 較該流體（C)低之流體（D)、與碳數4之烴濃度較該流體（〇 I低之流體（E)，將上述流體（d)回收至反應器，將上述流體 (E)自該製程取出之步驟。 I 〇·如申請專利範圍第8或9項之丙烯之製造方法，其 中’上述反應裔包括串聯連接的二個以上的反應部；將上 述供給至反應器之碳數4以上之烯烴原料、甲醇及二曱基 鍵中之至少一者、以及所回收之含烴流體（D)中之至少一 者’分割為第1階段反應部與第2階段以後之反應部而進 行供給。 II ·如申請專利範圍第8至10項中任一項之丙烯之製造 312XP/發明說明書(補件)/97-01/96135332 62 200831453 二%::1 料將上述流體⑻供給至蒸氣裂解製程，… 12如古申請專利範圍第n項之丙婦之製造方法，其中’ 之至少一部分與氫化觸媒接觸後，供給矣 瘵乳裂解製程。 ，如申請專利範圍第8至12項中任—項之丙烯之製造 士中，上述流體⑻所含之芳香族化合物濃度的合 寸為未滿5 · 〇體積％。 如中請專利範圍第8至13項中任—項之丙烯之製造 /其中’將上述流體⑻混合至蒸氣裂解製程之分解 汽油餾分中。 15. 如中請專利範圍第8至14項中任—項之丙烯之製造 =’其中〔上述流體⑻所含之碳數4之烴的合計濃度 為未滿5重量％。 16. 如申請專利範圍第8至15項中任—項之丙烯之製造 2法，其中，#由控制上述流體⑻及上述流體⑻之流 篁，而將上述供給至反應器之總原料中所含之碳數4以上 之稀烴與甲醇與二甲基鍵的合計濃度（基質濃度）控制於 20體積％以上且80體積％以下。 17. -種丙烯之製造方法，係將含有碳數4以上 烴、與甲醇及二甲基财之至少一者的混合物，於觸媒存 在下，在反應益中接觸而製造丙烯者；其特徵為，包括 有以下步驟（1)、（2)及（3B)之製程； 步驟⑴：將碳數4以上之稀烴原料、自步驟⑽所回 312XP/發明說明書(補件)/97-01/96135332 63 200831453 收之烴流體（i)、暨曱醇及二曱基醚中之至少一者，供給 至反應器，依反應器出口之碳數4以上之烯烴之莫耳流量 相對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 •丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體（反 應器出口氣體）之步驟； 步驟（2) ··將來自上述步驟（1)之反應器出口氣體，分離 (為富含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（A)、及富含水之流體之步驟； 步驟（3B):將上述步驟（2)中之流體（A)，分離為芳香族 化合物濃度較流體（A)低之流體（G)、與碳數4之烴濃度較 流體（A)低之流體（F)，將上述流體（G)之至少一部分^(1) 回收至反應器之步驟。 18· —種丙烯之製造方法，係將含有碳數4以上之烯 煙、與甲醉及二曱基鱗中之至少一者的混合物，於觸媒存 ϋ在下，在反應器中接觸而製造丙烯者；其特徵為包括含有 以下步驟（1)、（2)及（3Β)之製程； 步驟（1):將碳數4以上之烯烴原料、自步驟（3Β)所回 收之烴流體（I)、暨甲醇及二甲基醚中之至少一者供給至 反應益，依反應器出口之碳數4以上之烯烴之莫耳流量相 對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 丙烯與其他_、石虫論、芳香族化合物及水的氣體（反 應器出口氣體）之步驟； 312ΧΡ/發明說明書(補件)/97-01/96135332 64 200831453 步驟（2):將來自上述步驟（i)之反應器出口氣體，分離 為富含碳數3以下之烴的流體、富含碳數4以上之烴的流 體（A)、及富含水之流體之步驟； 步驟（3B):將上述步驟（2)中之流體（A)，分離為芳香族 化合物濃度較流體（A)低之流體（G)、與碳數4之烴濃度較 流體（A)低之流體（F)，將上述流體（F)自該製程取出，並 將上述流體（G)之一部分（I)回收至反應器，並將剩餘的流 體（H)自該製程取出之步驟。 19·如申請專利範圍第I?或18項之丙烯之製造方法， 其中，上述反應裔包括串聯連接的二個以上的反應部；將 上述供給至反應為之碳數4以上之烯烴原料、甲醇及二曱 基醚中之至少一者、以及所回收之含烴流體（I)中之至少 一者，分割為第1階段反應部與第2階段以後之反應部而 進行供給。 20.如申請專利範圍第17至19項中任一項之丙烯之製 造方法，其中，將上述流體（H)供給至蒸氣裂解製程，利 用作為裂解原料。 20項之丙稀之製造方法，其中， 部分與氳化觸媒接觸後，供給至 21·如申請專利範圍第 使上述流體（H)之至少一 蒸氣裂解製程。 =如申^專㈣圍第17至21項中任—項之丙稀之製 為未ΐ =述流體⑻所含之芳香族化合物濃度的 口汁為未滿5.0體積％。 製 23.如申請專利範圍第17至22項中任一項之丙稀之 312ΧΡ/^_^書(補件)/97·01/96135332 65 200831453 造方法，其中，將上述流體（F)混合至蒸氣裂解製程之分 解汽油館分中。 • &amp; 24·如申π專利範圍第丨7至23項中任一項之丙稀之製 ,&amp;方法，其中，上述流體（F)所含之碳數4之烴的合計濃 度為未滿5重量％。 、&amp;25·如申請專利範圍第17至24項中任一項之丙烯之製 造方法，其中，藉由控制上述流體（F)及流體（H)之流量， 广而將上述供給至反應器之總原料中所含之碳數4以上之 烯烴與甲醇與二曱基醚的合計濃度（基質濃度）控制於20 體積％以上且80體積％以下。 26·如申請專利範圍第8至25項中任一項之丙烯之製造 方法’其中，上述步驟（2)係包含藉由冷卻及壓縮步驟而 將水分自上述反應器出口氣體凝縮去除後，藉由蒸餾，分 離為富含碳數2以下之烴的流體與富含碳數3以上之烴的 流體’將上述富含碳數3以上之烴的流體藉蒸餾分離為富 (j含奴數3之煙的流體、與富含碳數4以上之煙的流體之步 27·如申請專利範圍第8至25項中任一項之丙烯之製造 方法，其中，上述步驟（2)係包含藉由冷卻及壓縮步驟而 • 將水分自上述反應器出口氣體凝縮去除後，藉由蒸餾，分 離為富含碳數3以下之烴的流體與富含碳數4以上之烴的 流體，將上述富含碳數3以下之烴的流體藉蒸餾分離為富 含碳數2以下之烴的流體與富含碳數3之烴的流體之步 驟。 312XP/發明說明書(補件)/97-01/96135332 66 200831453 28·如申請專利範圍第8至25項中任一項之丙烯之製造 方法’其中，上述步驟（2)係包含藉由冷卻及壓縮步驟而 將水分自上述反應器出口氣體凝縮去除後，藉由蒸餾，分 離為富含碳數2以下之烴的流體及富含碳數3之烴的流體 及富含碳數3以上之烴的流體，將上述富含碳數3以上之 煙的流體藉蒸餾分離為富含碳數3之烴的流體與富含碳 數4以上之烴的流體之步驟。 29·如申請專利範圍第8至25項中任一項之丙烯之製造 方法，其中，上述步驟（2)係包含藉由冷卻及壓縮步驟而 將水分自上述反應器出口氣體凝縮去除後，藉由蒸餾，分 離為使富含碳數3以下之烴的流體與富含碳數4以上之烴 的流體，將上述富含碳數3以下之烴的流體藉蒸餾分離為 含有碳數2以下之烴及碳數3之烴的流體、與富含碳數3 之烴的流體之步驟。 30·如申請專利範圍第8至29項中任一項之丙烯之製造 方法，其中，上述碳數4以上之烯烴原料係含有碳數4以 上之石蠟類。 31·如申請專利範圍第3〇項之丙烯之製造方法，其中， 上述石蝶類係含有正丁烷及異丁烷中之至少一者。 32·如申請專利範圍第8至31項中任一項之丙烯之製造 方法，其中，上述供給至反應器之原料中含有丁二烯。 33·如申請專利範圍第8至32項中任一項之丙烯之製造 =法，其中，於上述供給至反應器之總原料中所含之芳香 族化合物的合計量，相對於該總原料所含之碳數4以上之 67 (補件)/97G1/96i3知2 200831453 烯烴的合計量，以莫耳比計為未滿〇 〇5。 34·如申請專利範圍第8至33項中任一項之丙烯之製造 f/去#中’上述供給至反應器之碳&amp; 4以上之稀煙的 量，相對於該供給至反應器之甲醇莫耳數與二甲基鱗莫耳 數之2倍的合計’以莫耳比計為0·2以上且以下。 35·如申請專利範圍第8至34項中任一項之丙烯之製造 方法，其中，上述供給至反應器之碳數4以上之烯烴原 p料，係含有由蒸氣裂解製程所得之碳數4之烴流體。 /6· —種丙烯之製造方法，係將含有碳數4以上之烯 經、與甲醇及二甲基謎中之至少一者的混合物，於觸媒存 在下，在反應器中接觸而製造丙烯者；其特徵為，包括含 有以下步驟（1C)、（2C)、（3C)及（4C)之製程； 步驟（1C):將碳數4以上之烯烴原料、自步驟（4C)所回 收之烴流體（Q)、暨曱醇及二曱基醚中之至少一者供給至 反應器，依反應器出口之碳數4以上之烯烴之莫耳流量相 對於反應器入口之該烯烴之莫耳流量為2〇%以上且未滿 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體（反 應器出口氣體）之步驟； ，步驟（2C):將來自上述步驟（iC)之反應器出口氣體冷 卻’为離為氣體流體（L )、富含碳數4以上之煙並含有芳 香族化合物的液流體（Μ )、及富含水之流體之步驟； 步驟（3C):將上述步驟（2C)中之氣體流體（L)分離為富 含碳數3以下之經的流體與富含碳數4以上之烴的流體（ν ) 3 UXP/發明說明書(補件)/97-01/96135332 68 200831453 之步驟； 步驟（4C):將上述流體（N)之至少一部分流體（Q)回收至 反應器之步驟。 37. —種丙烯之製造方法，係將含有碳數4以上之烯 烴、與甲醇及二曱基醚中之至少一者的混合物，於觸媒存 在下，在反應器中接觸而製造丙烯者；其特徵為，包括含 有以下步驟（1C)、（2C)、（3C)及（4C)之製程； 步驟（1C) ··將碳數4以上之烯烴原料、自步驟（4C)所回 1 收之烴流體（Q)、暨曱醇及二甲基醚中之至少一者供給至 反應器，依反應器出口之碳數4以上之烯烴之莫耳流量相 對於反應器入口之該烯烴之莫耳流量為20%以上且未滿 90%的反應條件，與觸媒接觸，而自反應器出口得到含有 丙烯與其他烯烴、石蠟類、芳香族化合物及水的氣體（反 應器出口氣體）之步驟； 步驟（2C):將來自上述步驟（1C)之反應器出口氣體冷 I卻，藉壓縮將冷卻後之氣體流體（K)分離為氣體流體（L)、 富含碳數4以上之烴並含有芳香族化合物的液流體（M)、 及富含水之流體之步驟； 步驟（3C):將上述步驟（2C)中之氣體流體（L)分離為富 含碳數3以下之烴的流體與富含碳數4以上之烴的流體（N) 之步驟； 步驟（4C):將上述流體（N)之一部分（P)自該製程取出， 將剩餘的流體（Q)回收至反應器之步驟。 38. 如申請專利範圍第36或37項之丙烯之製造方法， 312XP/發明說明書(補件)/97-01/96135332 69 200831453 其中，藉蒸餾將上述液流體（Μ)分離為芳香族化合物濃度 較液流體（Μ)中低之流體（R)與碳數4之烴濃度較液流體 (Μ)低之流體（S)。 39. 如申請專利範圍第38項之丙烯之製造方法，其中， 將上述流體（R)送回至從上述流體（Κ)、（L)、（Μ)、（Ρ)及 (Q)中選出之任一或二以上的流體的流通處。 40. 如申請專利範圍第36至39項中任一項之丙烯之製 造方法，其中，上述步驟（3C)係包含藉由蒸餾將上述氣體 流體（L)分離為富含碳數2以下之烴的流體與富含碳數3 以上之烴的流體，並進一步藉蒸餾將富含碳數3以上之烴 的流體分離為富含碳數3之烴的流體與富含碳數4以上之 烴的流體（Ν)之步驟。 41. 如申請專利範圍第36至39項中任一項之丙烯之製 造方法，其中，上述步驟（3C)係包含藉由蒸餾將上述氣體 流體（L)分離為富含碳數3以下之烴的流體與富含碳數4 以上之烴的流體（Ν)，並進一步藉蒸餾將富含碳數3以下 之烴的流體分離為富含碳數2以下之烴的流體與富含碳 數3之烴的流體之步驟。 42. 如申請專利範圍第36至39項中任一項之丙烯之製 造方法，其中，上述步驟（3C)係包含藉由蒸餾將上述氣體 流體（L)分離為含有碳數2以下之烴與碳數3之烴的流 體、及富含碳數3以上之烴的流體，並進一步藉蒸餾將富 含碳數3以上之烴的流體分離為富含碳數3之烴的流體與 富含碳數4以上之烴的流體（Ν)之步驟。 312ΧΡ/發明說明書(補件)/97-01/96135332 70 200831453 43.如申請專利範圍第36至39項中任一項之丙烯之製 k方法，其中，上述步驟（3C)係包含藉由蒸餾將上述氣體 μ體（L)分離為富含碳數3以下之烴的流體與富含碳數4 以上之烴的流體（Ν)，並進一步藉蒸餾將富含碳數3以下 之工的々丨L體刀離為含有碳數2以下之烴與碳數3之烴的流 體、及虽含碳數3之烴的流體之步驟。 α44.如申請專利範圍第36至43項中任一項之丙烯之製 方法/、中，上述反應器包括串聯連接的二個以上的反 '應部；將上述供給至反應器之碳數4以上之烯烴原料、曱 醇及二甲基驗中之至少一者、暨所回收之含烴流體中之至 少一者，分割為第丨階段反應部與第2階段以後之反應部 而進行供給。 u 、α45.如申請專利範圍第36至44項中任一項之丙烯之製 以方法，其中，上述碳數4以上之烯烴原料係含有碳數4 以上之石壤類。 L) 46·如申請專利範圍第45項之丙烯之製造方法，其申， 上述石蠟類係含有正丁烷及異丁烷中之至少一者。/、 、生47·、如申明專利範圍第36至46項中任一項之丙稀之製 &amp;方法，其中，於上述供給至反應器中之原料中含有丁一 稀。 q j — /•、如中請專利範圍第36至47項中任—項之丙稀之製 法，其中，於上述供給至反應器之總原料中所含之 香族化合物的合計量，相對於該總原料所含之碳數 之婦煙的合計量，以莫耳料為未滿0.05。 312XP/^_ 明書(補件)/97-01/96135332 200831453 /9·如申請專利範圍第36至⑼項中^項之丙稀之製 造方法，其中，將上述流體（M)及上述流體（p)中之至少一 者供給至蒸氣裂解製程，利用作為裂解原料。 50.如申請專利範圍第49項之丙烯之製造方法，其中， 使上述流體（M)及上述流體（p)中之至少一者的至少一部 分與氫化觸媒接觸後，供給至蒸氣裂解製程。 、止51·、如申請專利範圍第36至5G項中任一項之丙稀之製 造I法，其中，上述流體（M)及上述流體（p)中之至少一者 所含之芳香族化合物濃度的合計為未滿5 〇體積％。 生52:如中請專利範圍第36至51項中任—項之丙稀之製 —法其中，將上述流體（M)混合至蒸氣裂解製程之分 解汽油館分中。 /3.如中請專利範圍第36至52項中任—項之丙稀之製 f方法、’其中’上述流體⑻所含之碳數4之烴的合計濃 度為未滿5重量％。 (J /4·如申請專利第36至53項中任—項之丙稀之製 j方法’其中，藉由控制上述流體（Μ)及上述流體⑺之流 里’而將上述供給至反應器之總原料中所含之碳數4以上 之與甲醇與二甲基㈣合計濃度（基質濃度）控制於 20體積％以上且8〇體積％以下。 、α55\如申請專利範圍第38至54項中任一項之丙烯之製 法，其中，將上述流體（R)供給至蒸氣裂解製程，利 用作為裂解原料。 士申明專利範圍第55項之丙烯之製造方法，其中， 312XP/發明說明書(補件)/97-01/96135332 72 200831453 一部分與氫化觸媒接觸後，供給至 使上述流體（R )之至少 蒸氣裂解製程。 、止57·、如中請專利範圍第⑽至⑽項中任一項之丙稀之製 k方法’丨中’上述流體⑻中所含之芳香族化合物濃度 的合計為未滿5· 0體積％。 、止58.、如申請專利範圍帛38至57項中任一項之丙稀之製200831453 X. Patent application scope: 1. A method for manufacturing propylene, which is a raw material containing carbon number and sterol and didecyl ether to small soil t 丄 &lt; lung/work H to J Producing propylene in contact with a reactor in the presence of a catalyst; characterized in that at least one of the aromatic compounds contained in the r-claw® pore (reactor outlet gas) is discharged from the outlet of the reactor. A part is taken out, and at least a portion of the olefin of =4 or more contained in the gas (reactor outlet gas) is discharged from the reaction II outlet, and is again contacted with the medium (4). 2. The method for producing propylene according to item i of the patent application, wherein the olefin raw material having 4 or more carbon atoms is a paraffin having 4 or more carbon atoms. 3. The method for producing propylene according to item 2 of the patent scope, wherein the paraffin wax contains at least one of n-butane and isobutane. 4. The method for producing propylene according to any one of claims 4 to 3, wherein the raw material supplied to the reactor contains dibutyl slag. (5) The method for producing propylene according to any one of the above-mentioned claims, wherein the total amount of the aromatic compound contained in the total raw material supplied to the reactor is relative to the total raw material The method for producing propylene according to any one of the above-mentioned claims, wherein the above-mentioned supply is the same as the molar ratio of the olefin having a carbon number of 4 or more. The amount of the olefin having a carbon number of 4 or more to the reactor is 〇·2 or more in terms of a molar ratio with respect to the total of the number of moles of methanol supplied to the reactor and the number of moles of dimethyl ether. 1〇以下. 7. Manufacture of propylene according to any one of claims 1 to 6 of the patent application 312ΧΡ/invention specification (supplement)/97_〇1/96135332 60 200831453 method 'where' supply of the above to the reaction The total concentration (base concentration) of the hydrocarbons having a carbon number of 4 or more and the methanol and the ruthenium fluorene contained in the total raw material of the apparatus is controlled to be 20% by volume or more and 8% by volume or less. The method 'will contain a dilute hydrocarbon of 4 or more, and methanol and dimethyl ether. a raw material of lesser one, which is contacted in a reactor to produce propylene in the presence of a catalyst; and is characterized by comprising a process comprising the following steps (1), (2) and (3A); (Step (1): At least one of the olefin raw material having a carbon number of 4 or more, the hydrocarbon fluid (D) recovered from the step (3A), and methanol and dimethyl ether is supplied to the reactor, and the carbon number of the outlet of the reactor is 4 or more. The molar flow rate of the olefin is 2% by mole or more and less than 90% of the reaction conditions of the olefin at the inlet of the reactor, and is contacted with the above-mentioned catalyst, and the propylene and other olefins and paraffins are obtained from the outlet of the reactor. a step of a gas of a class, an aromatic compound and water (reactor outlet gas); step (2) · separating a gas from the reactor outlet gas of the above step (1) into a fluid rich in hydrocarbons having a carbon number of 3 or less a fluid (A) rich in carbon 4 or more hydrocarbons, and a step of enriching the water; step (3A) · · at least a part of the fluid (C) of the fluid (A) in the above step (2) 'Separated as a fluid with a lower aromatic concentration than the fluid (c) • (D), a step (C) of recovering the fluid (D) from the fluid (E) having a lower hydrocarbon concentration than the fluid (C), and recovering the fluid (E) from the process. A method for producing propylene, which comprises a raw material containing at least one of a olefin having a carbon number of 4 or more and methanol and a dimethyl ether in the presence of a catalyst, 312XP/invention specification (supplement)/97-01/ 96135332 61 200831453 Producing propylene by contact in a reactor; characterized by comprising a process comprising the following steps (1), (2) and (3A); eve step (1): olefin raw material having a carbon number of 4 or more, At least one of the hydrocarbon fluid (D), cuminol and dimethyl ether recovered in the step (3A) is supplied to the reactive genus. The reaction conditions of the olefin at the inlet of the reactor are 2% by mole or more and less than 90%, and the catalyst is contacted with the catalyst, and the plant is supplied with propylene and other olefins, paraffins, aromatic compounds and Water gas (reactor outlet gas) step; step (2): will come from above step(! The reactor outlet gas is separated into a fluid rich in carbon atoms of 3 or less, a fluid (A) rich in carbon 4 or more, and a water-rich fluid; Step (3A) · · Part (8) of the fluid (A) in the above step (2) is taken out from the process 'separating the remaining fluid (c) into a fluid (D) having a lower aromatic compound concentration than the fluid (C), and carbon The hydrocarbon concentration of the number 4 is lower than the fluid (E), the fluid (d) is recovered to the reactor, and the fluid (E) is taken out from the process. I 〇· The method for producing propylene according to item 8 or 9, wherein the above-mentioned reactants include two or more reaction portions connected in series; and at least the olefin raw materials, methanol and dimercapto bonds having a carbon number of 4 or more supplied to the reactor At least one of the recovered hydrocarbon-containing fluid (D) is divided into a first-stage reaction unit and a reaction unit after the second stage. II. As in the patent scopes 8 to 10 Manufacture of propylene 312XP / invention manual (supplement) / 97-01/96135332 62 200831453 2%::1 The above-mentioned fluid (8) is supplied to the steam cracking process, ... 12 The method for manufacturing the B-wife of the nth item of the patent application, wherein at least a part of the contact with the hydrogenation catalyst is supplied to the milk The cleavage process, as in the manufacture of propylene of any of the items 8 to 12 of the patent application, the concentration of the aromatic compound contained in the fluid (8) is less than 5 · 〇 vol%. Manufacture of propylene according to any of items 8 to 13 / wherein 'mixing the above fluid (8) into the decomposition gasoline fraction of the steam cracking process. 15. propylene according to any of the claims 8 to 14 Manufactured = 'wherein the total concentration of the hydrocarbons having a carbon number of 4 contained in the fluid (8) is less than 5% by weight. 16. The method for producing propylene according to any one of claims 8 to 15, wherein , by controlling the flow of the fluid (8) and the fluid (8), the total concentration (base concentration) of the hydrocarbon having a carbon number of 4 or more and the methanol and the dimethyl bond contained in the total raw material supplied to the reactor. Controlled to 20% by volume And 80% by volume or less. 17. A method for producing propylene, which comprises a mixture of a hydrocarbon having 4 or more carbon atoms and at least one of methanol and dimethyl group, in the presence of a catalyst, in contact with the reaction And the manufacture of propylene; characterized by comprising the following steps (1), (2) and (3B); step (1): using a carbon number of 4 or more of the dilute hydrocarbon raw material, from step (10) back to 312XP / invention specification ( Supplement) /97-01/96135332 63 200831453 At least one of the hydrocarbon fluid (i), cuminol and dimethyl ether is supplied to the reactor, and the number of olefins having a carbon number of 4 or more depending on the outlet of the reactor The molar flow rate of the olefin with a molar flow rate of 2% or more and less than 90% with respect to the inlet of the reactor is in contact with the catalyst, and the propylene and other olefins and paraffins are obtained from the outlet of the reactor. Step of aromatic gas and water gas (reactor outlet gas); Step (2) · Separating the outlet gas of the reactor from the above step (1) (for a fluid rich in hydrocarbons having a carbon number of 3 or less, rich Fluid (A) containing hydrocarbons having a carbon number of 4 or more, and water-rich Step of fluid; Step (3B): separating the fluid (A) in the above step (2) into a fluid (G) having a lower aromatic compound concentration than the fluid (A) and a hydrocarbon having a carbon number of 4 (compared to a fluid having a carbon number of 4) A) A low fluid (F), the step of recovering at least a portion (1) of the above fluid (G) to the reactor. 18. A method for producing propylene, which comprises producing a mixture of at least one of a olefinic ketone having a carbon number of 4 or more and a guanidinium and a ruthenium sulphate, which is placed in a reactor under contact with a catalyst. a propylene; characterized by comprising a process comprising the following steps (1), (2) and (3); step (1): a hydrocarbon having a carbon number of 4 or more, a hydrocarbon fluid recovered from the step (3) (I) And at least one of methanol and dimethyl ether is supplied to the reaction benefit, and the molar flow rate of the olefin of the carbon number of 4 or more according to the outlet of the reactor is 2% by mole relative to the molar flow rate of the olefin of the reactor inlet. Above and below 90% of the reaction conditions, contact with the catalyst, and a step of obtaining a gas containing propylene and other _, stoneworm, aromatic compound and water (reactor outlet gas) from the outlet of the reactor; 312 ΧΡ / invention Specification (supplement)/97-01/96135332 64 200831453 Step (2): Separating the outlet gas of the reactor from the above step (i) into a fluid rich in hydrocarbons having a carbon number of 3 or less, and having a carbon number of 4 or more Hydrocarbon fluid (A), and water-rich fluid steps; Step (3B): separating the fluid (A) in the above step (2) into a fluid having a lower concentration of the aromatic compound than the fluid (A) and a lower concentration of the hydrocarbon having a carbon number of 4 than the fluid (A) Fluid (F), the step of taking out the above fluid (F) from the process, and recovering part (I) of the above fluid (G) to the reactor, and taking out the remaining fluid (H) from the process. 19. The method for producing propylene according to claim 1 or 18, wherein the reactant includes two or more reaction units connected in series; and the olefin raw material and methanol supplied to the reaction having a carbon number of 4 or more are supplied. At least one of the dimercaptoether and at least one of the recovered hydrocarbon-containing fluids (I) are divided into a first-stage reaction unit and a reaction unit after the second stage and supplied. The method for producing propylene according to any one of claims 17 to 19, wherein the fluid (H) is supplied to a steam cracking process and used as a cracking raw material. A method for producing propylene of 20, wherein, after being partially contacted with a bismuth catalyst, it is supplied to 21% of the vapor cracking process of the fluid (H) as claimed in the patent application. = 丙 之 专 申 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ 23. The method of manufacturing a fluid (F) according to any one of the claims pp. 17 to 22, 312 ΧΡ / ^_^ (supplement) / 97·01/96135332 65 200831453 To the decomposition of gasoline in the steam cracking process. &amp; 24. The propylene system according to any one of claims 7 to 23, wherein the total concentration of hydrocarbons having a carbon number of 4 contained in the fluid (F) is not 5% by weight. The method for producing propylene according to any one of claims 17 to 24, wherein the above is supplied to the reactor by controlling the flow rates of the fluid (F) and the fluid (H) The total concentration (base concentration) of the olefin having a carbon number of 4 or more and the methanol and the dimethyl ether contained in the total raw material is controlled to be 20% by volume or more and 80% by volume or less. The method for producing propylene according to any one of claims 8 to 25, wherein the step (2) comprises condensing and removing moisture from the outlet gas of the reactor by a cooling and compression step, By distillation, the fluid separated into a hydrocarbon having a carbon number of 2 or less and a fluid having a hydrocarbon having a carbon number of 3 or more 'separate the above-mentioned fluid having a carbon number of 3 or more by distillation into a rich (j) The method for producing a propylene according to any one of claims 8 to 25, wherein the step (2) comprises Cooling and compression steps. • After the water is condensed and removed from the outlet gas of the reactor, it is separated into a fluid rich in carbon atoms of 3 or less and a fluid rich in hydrocarbons having 4 or more carbons by distillation. The fluid of a hydrocarbon having a carbon number of 3 or less is separated by distillation into a fluid having a hydrocarbon having a carbon number of 2 or less and a fluid having a hydrocarbon having a carbon number of 3. The 312XP/Invention Manual (Supplement)/97-01/96135332 66 200831453 28·If you apply for any of the patent scopes 8 to 25 The method for producing a olefin, wherein the step (2) comprises condensing and removing water from the outlet gas of the reactor by a cooling and compression step, and then separating into a fluid having a hydrocarbon having a carbon number of 2 or less by distillation and a fluid rich in carbon number 3 hydrocarbons and a fluid rich in hydrocarbons having a carbon number of 3 or more, and the above-mentioned fluid rich in carbon 3 or more is separated into a fluid rich in carbon number 3 and rich in carbon by distillation The method for producing a propylene having a hydrocarbon number of 4 or more. The method for producing propylene according to any one of claims 8 to 25, wherein the step (2) comprises water from a cooling and compression step. After the reactor outlet gas is condensed and removed, it is separated into a fluid having a hydrocarbon having a carbon number of 3 or less and a fluid having a carbon number of 4 or more by distillation, and the fluid having a hydrocarbon having a carbon number of 3 or less is used. A step of separating into a fluid containing a hydrocarbon having a carbon number of 2 or less and a hydrocarbon having a carbon number of 3 and a fluid having a hydrocarbon having a carbon number of 3 by distillation. 30. The propylene according to any one of claims 8 to 29 Manufacturing method in which the above olefin having 4 or more carbon atoms The method of producing a propylene according to the third aspect of the invention, wherein the stone butterfly type contains at least one of n-butane and isobutane. The method for producing propylene according to any one of claims 8 to 31, wherein the raw material supplied to the reactor contains butadiene. 33. According to any one of claims 8 to 32. The production of propylene = method, wherein the total amount of the aromatic compound contained in the total raw material supplied to the reactor is 67 or more (supplement) / 97G1/96i3 with respect to the carbon number of the total raw material of 4 or more知2 200831453 The total amount of olefins is less than 莫5 in terms of molar ratio. 34. The manufacture of propylene in any one of claims 8 to 33, wherein the amount of the above-mentioned lean carbon of the carbon &amp; 4 supplied to the reactor is relative to the supply to the reactor The total of the methanol molar number and the dimethyl scale molar number twice is 0. 2 or more and the following by the molar ratio. The method for producing propylene according to any one of claims 8 to 34, wherein the olefin raw material of the carbon number of 4 or more supplied to the reactor contains the carbon number obtained by the steam cracking process 4 Hydrocarbon fluid. /6· A method for producing propylene, which comprises reacting a mixture containing at least one of a carbon number of 4 or more with methanol and a dimethyl mystery in a reactor to produce propylene. And characterized in that it comprises a process comprising the following steps (1C), (2C), (3C) and (4C); Step (1C): recovering the olefin raw material having a carbon number of 4 or more and recovering from the step (4C) At least one of a hydrocarbon fluid (Q), cumol, and dimethyl ether is supplied to the reactor, and the molar flow of the olefin having a carbon number of 4 or more depending on the outlet of the reactor is relative to the mole of the olefin at the inlet of the reactor a reaction step of contacting a catalyst with a flow rate of 2% or more and less than 90%, and obtaining a gas containing propylene and other olefins, paraffin, aromatic compound, and water (reactor outlet gas) from the outlet of the reactor Step (2C): cooling the reactor outlet gas from the above step (iC) as a liquid fluid (Μ) which is a gas fluid (L), is rich in carbon 4 or more, and contains an aromatic compound, And a step of enriching the water; step (3C): taking the above steps The gas fluid (L) in (2C) is separated into a fluid having a carbon number of 3 or less and a fluid having a carbon number of 4 or more (ν) 3 UXP/Invention Manual (Supplement)/97-01/ 96135332 68 steps of 200831453; Step (4C): a step of recovering at least a portion of the fluid (Q) of the above fluid (N) to the reactor. 37. A method for producing propylene, which comprises contacting a mixture of an olefin having 4 or more carbon atoms and at least one of methanol and dimercapto ether in a reactor to produce propylene; It is characterized in that it comprises a process comprising the following steps (1C), (2C), (3C) and (4C); Step (1C) ·· The olefin raw material having a carbon number of 4 or more is recovered from the step (4C) At least one of a hydrocarbon fluid (Q), cumol, and dimethyl ether is supplied to the reactor, and the molar flow of the olefin having a carbon number of 4 or more depending on the outlet of the reactor is relative to the olefin of the reactor inlet a step of contacting the catalyst with an ear flow rate of 20% or more and less than 90%, and obtaining a gas containing propylene and other olefins, paraffins, aromatic compounds, and water (reactor outlet gas) from the outlet of the reactor Step (2C): cooling the outlet gas of the reactor from the above step (1C), and separating the cooled gaseous fluid (K) into a gaseous fluid (L), a hydrocarbon having a carbon number of 4 or more by compression Liquid fluid (M) containing aromatic compounds, and water-rich fluid Step; Step (3C): a step of separating the gas fluid (L) in the above step (2C) into a fluid having a carbon number of 3 or less and a fluid (N) having a hydrocarbon having a carbon number of 4 or more; (4C): a step of taking out a part (P) of the above fluid (N) from the process and recovering the remaining fluid (Q) to the reactor. 38. The method for producing propylene according to claim 36 or 37, 312XP/invention specification (supplement)/97-01/96135332 69 200831453 wherein the liquid fluid (Μ) is separated into aromatic compounds by distillation The fluid (R) which is lower in the liquid fluid (Μ) and the fluid (S) in which the hydrocarbon concentration of the carbon number 4 is lower than that of the liquid fluid (Μ). 39. The method for producing propylene according to claim 38, wherein the fluid (R) is returned to the fluids (Κ), (L), (Μ), (Ρ), and (Q). The circulation of any or more of the fluids. The method for producing propylene according to any one of claims 36 to 39, wherein the step (3C) comprises separating the gas fluid (L) into a hydrocarbon having a carbon number of 2 or less by distillation. a fluid and a fluid rich in hydrocarbons having a carbon number of 3 or more, and further separating, by distillation, a fluid having a carbon number of 3 or more hydrocarbons into a fluid having a carbon number of 3 and a hydrocarbon having a carbon number of 4 or more The step of fluid (Ν). The method for producing propylene according to any one of claims 36 to 39, wherein the step (3C) comprises separating the gas fluid (L) into a hydrocarbon having a carbon number of 3 or less by distillation. a fluid with a hydrocarbon having a carbon number of 4 or more (Ν), and further separating a fluid having a carbon number of 3 or less into a fluid having a carbon number of 2 or less and a carbon-rich number 3 by distillation The step of the fluid of the hydrocarbon. The method for producing propylene according to any one of claims 36 to 39, wherein the step (3C) comprises separating the gas fluid (L) into a hydrocarbon having a carbon number of 2 or less by distillation. a hydrocarbon having a carbon number of 3 and a fluid having a hydrocarbon having a carbon number of 3 or more, and further separating a fluid having a carbon number of 3 or more by a distillation into a fluid rich in carbon number 3 and rich in carbon The step of a fluid (Ν) of a hydrocarbon number of 4 or more. The method of producing propylene according to any one of claims 36 to 39, wherein the above step (3C) comprises distillation by distillation. Separating the above gas μ body (L) into a fluid rich in carbon atoms of 3 or less and a fluid having a carbon number of 4 or more, and further enriching the carbon having a carbon number of 3 or less by distillation The 丨L body blade is a step of containing a fluid having a carbon number of 2 or less and a hydrocarbon having 3 carbon atoms, and a fluid containing a hydrocarbon having 3 carbon atoms. The method for producing propylene according to any one of claims 36 to 43 wherein the reactor comprises two or more opposite portions connected in series; and the carbon number supplied to the reactor is 4 At least one of the above olefin raw material, sterol and dimethyl alcohol, and at least one of the recovered hydrocarbon-containing fluids are divided into a second-stage reaction unit and a reaction unit after the second stage. The method for producing propylene according to any one of claims 36 to 44, wherein the olefin raw material having a carbon number of 4 or more contains a stone having a carbon number of 4 or more. The method for producing propylene according to claim 45, wherein the paraffin wax contains at least one of n-butane and isobutane. The method of propylene according to any one of claims 36 to 46, wherein the raw material supplied to the reactor contains dilute. Qj — /•, as in the method of propylene according to any one of claims 36 to 47, wherein the total amount of the aromatic compound contained in the total raw material supplied to the reactor is relative to the The total amount of cigarettes contained in the total amount of raw materials is less than 0.05 in terms of moles. 312XP/^_明书(补件)/97-01/96135332 200831453 /9. The manufacturing method of the propylene according to Item 36 to (9) of the patent application, wherein the fluid (M) and the fluid are At least one of (p) is supplied to a steam cracking process and utilized as a cracking feedstock. The method for producing propylene according to claim 49, wherein at least a part of at least one of the fluid (M) and the fluid (p) is brought into contact with a hydrogenation catalyst, and then supplied to a vapor cracking process. The method of manufacturing propylene according to any one of claims 36 to 5G, wherein the aromatic compound contained in at least one of the fluid (M) and the fluid (p) The total concentration is less than 5% by volume. Health 52: In the case of the propylene system of the scope of the patent range 36-51, the above fluid (M) is mixed into the gasoline decomposition process of the steam cracking process. /3. The method of propylene according to any one of claims 36 to 52, wherein the total concentration of hydrocarbons having a carbon number of 4 contained in the fluid (8) is less than 5% by weight. (J/4. The method of propylene according to any one of claims 36 to 53) wherein the above is supplied to the reactor by controlling the flow of the fluid (Μ) and the fluid (7) The total carbon content of 4 or more and the total concentration of methanol and dimethyl (tetra) (matrix concentration) are controlled to be 20% by volume or more and 8% by volume or less. α55\, as disclosed in claims 38 to 54 The method for producing propylene according to any one of the preceding claims, wherein the fluid (R) is supplied to a steam cracking process and used as a cracking raw material. The method for producing propylene according to Item 55 of the patent specification, wherein 312XP/invention specification (supplement) ) /97-01/96135332 72 200831453 A part is contacted with a hydrogenation catalyst and supplied to at least a vapor cracking process of the above fluid (R)., 57., as in the patent scope (10) to (10) The acryl method k method '丨中' The total concentration of the aromatic compounds contained in the fluid (8) is less than 5.00 vol%, 58., as in the patent application 帛 38 to 57 The principle of ac ^法八中，將上述流體（S)混合至蒸氣裂解製程之分 解汽油顧分中。 止59:如巾請專·圍第38至58項巾任—項之丙稀之製 k方法，其中，上述流體（s)所含之碳數4之烴的合計濃 度為未滿5重量％。 、土 6〇.如申請專利範圍帛38至59項中任一項之丙烯之製 造方法，其中，藉由控制上述流體⑺、流體（R)及流體⑻ 之流量，而將上述供給至反應器之總補中所含之碳數4 以上之婦煙與曱醇與二甲基轉的合計濃度（基質濃度）控 制於20體積％以上且8〇體積％以下。 61·如申請專利範圍帛38至6〇項中任一項之丙稀之製 以方法其中，將上述流體（R)送回至從上述流體（κ)、 (L)二(Ν)、⑺及(Q)中選出之任一或二以上的流體的流通 處’猎由控制上述流體⑻之送回處及其流量，而將上述 供給至反應H之總原料中所含之碳數4以上之婦煙與甲 醇與二f基驗的合計濃度（基質濃度）控制於2()體積％以 上且80體積％以下。 項中任一項之丙烯之製 62·如申請專利範圍第36至6Ϊ 312ΧΡ/發明說明書(補件)/97-01/96135332 73 200831453 j方法’其中’上述供給至反應器之碳數4以上之烯烴的 里’相對於該供給至反應器之^醇莫耳數與二甲基謎莫耳 倍的17汁，以莫耳比計為〇. 2以上且1 〇以下。 、二如申甘請專利範圍第36至62項中任-項之丙烯之製 :，传含供給至反應器之碳數4以上之烯烴原 有由㈣裂解製程所得之碳數4之烴流體。 〇 312XP/發明說明書(補件)/97-01/96135332^法八中, mixing the above fluid (S) into the decomposition of gasoline in the steam cracking process.止59: For the towel, please use the method of the propylene method of the 38th to 58th items, wherein the total concentration of the hydrocarbons having the carbon number 4 contained in the fluid (s) is less than 5% by weight. . The method for producing propylene according to any one of claims 38 to 59, wherein the above is supplied to the reactor by controlling the flow rates of the fluid (7), the fluid (R) and the fluid (8) The total concentration (matrix concentration) of the cigarettes having a carbon number of 4 or more and the sterol and dimethyl group contained in the total amount is controlled to be 20% by volume or more and 8% by volume or less. 61. The method according to any one of claims 38 to 6, wherein the fluid (R) is returned to the fluid (κ), (L) two (Ν), (7) And the flow of the fluid selected in any one or more of (Q) is controlled by controlling the return of the fluid (8) and the flow rate thereof, and the carbon content contained in the total raw material supplied to the reaction H is 4 or more. The total concentration (matrix concentration) of the flue-cured tobacco and the methanol and the two-fractal test is controlled to 2% by volume or more and 80% by volume or less. Manufacture of propylene according to any one of the items 62. pp. 36 to 6 Ϊ 312 ΧΡ / invention specification (supplement) / 97-01/96135332 73 200831453 j method 'where 'the above carbon number supplied to the reactor is 4 or more The olefin of the olefin is relative to the 17 moles of the molar amount of alcohol supplied to the reactor and the dimethyl mystery molar ratio, and the molar ratio is 〇. 2 or more and 1 〇 or less. 2. For example, in the case of Shen Gan, the propylene system of any of the items 36 to 62 of the patent range: the hydrocarbon having a carbon number of 4 or more supplied to the reactor, and the hydrocarbon fluid having the carbon number of 4 obtained by the cracking process . 〇 312XP / invention manual (supplement) /97-01/96135332
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