丁二烯係石油化工之重要基本原料之一，目前全球主要來源係從輕油裂解之碳四餾分（C4 cut）中萃取蒸餾而得，也可以透過丁烯或丁烷之商業脫氫製程而得，而現有之丁烯商業脫氫製程技術已臻純熟，如飛利浦（Phillips）公司之“O-X-DTM process”脫氫製程、及Petro-Tex公司之“Oxo-DTM process”氧化脫氫製程等。 然而近年來由於其他石化能源、及頁岩氣之開發崛起，全球各煉油石化業不得不思考出路以因應煉製結構改變所帶來之市場衝擊。在大量傾向輕質組份進料之煉油裂解結構改變情況下，如甲烷、乙烷、丙烷、及乙烯等輕質產品之產量未來將可能會供過於求，相對的丙烯、丁烯、及丁二烯等乃至較重質之苯、甲苯、及二甲苯等石化原料產量將可能會供不應求。未來可能會演變成丙烯、丁烯、及丁二烯等市場價格飆升，而甲烷、乙烷、丙烷、及乙烯之市價下跌。 為了轉化乙烯成為四碳（或以上）之其他產物，乙烯齊聚、寡聚之方法在早期便已被廣泛研究，其最主要作用為製造生產直鏈α-烯烴（α-olefin），相關細節可參見台灣專利—TW223053B。如乙烯齊聚生產α-烯烴之反應程序現已有法國石油研究院（IFP）所開發之AlphaSelect技術、以及Gulf石油公司與Shell公司等相關生產技術。而乙烯雙聚法乃是屬於乙烯寡聚之範疇，其主要目的是為了生產丁烯、己烯。其中又以IFP/Axens之AlphaButol技術、與AlphaHexol技術較為著名，而AlphaButol係目前全球唯一已商業化利用乙烯聚合來生產丁烯之技術。 從反應動力學與輸送現象之角度來看，均相催化反應理論上會比異相催化反應效果佳，意即，液態觸媒之催化效能會比固態觸媒佳。就乙烯雙聚反應而言，IFP AlphaButol之專利US20140088331A1中曾以其液態觸媒與三井化學公司專利JP2011/148720中之固態觸媒進行優劣比較，其液態觸媒催化乙烯雙聚，乙烯轉化率為70～90 %，目標產物丁烯產率最佳為91 %；JP2011/148720中最佳例之固態觸媒之乙烯轉化率為49.5 %、丁烯之選擇率為79.4 %、產率為39.3 %。其他液態觸媒研究如Phillips公司之專利，US4528415A中之液相反應係在磷化氫等酸性物質添加條件下以鎳觸媒進行，其丁烯之選擇率可達81～98 %（碳四餾分中1-丁烯）。此外，近年來以固態觸媒催化乙烯寡聚技術也被積極研發中，如Bi Y. L.等人利用陶瓷合成法製備了La/Ba/Sm氧化物催化劑，在450～600°C之二氧化碳（CO2
）氣氛下進行氧化脫氫，其選擇性達到80 %，異丁烯之產率為22 %，此相關研究細節可參見論文一（Bi Y. L., Catal. Today, (2000), 61, 369-375）。專利US7847140B2中以NiSO4
/SiO2
-Al2
O3
（ALON）載體觸媒並透過催化蒸餾（Catalic distillation）技術進行模擬，其最佳乙烯轉化率為96.8 %，1-丁烯及1-己烯選擇率分別為60 %及40 %。 然而，就工業利用層面來看，現有商業技術之液相觸媒反應方式，其依然存在後續分離程序之問題，亦須將溶劑、及副產物等自產品中分離移除；且液態觸媒反應多採用氟化硼、氯化鋁與烷基鋁化物（如三乙基鋁(Aluminumtriethyl, TEA)、三丁基鋁）、或烷基鈦化物（如鈦酸四丁酯(Tetrabutyl titanate, TBT)）等作為催化劑，相關細節可參見專利—US20140088331A1、US4532370A、及US4615998A。上述該類型催化劑潛藏著燃燒、爆炸之安全疑慮。且液態觸媒殘留於產品中之金屬成分可能會侷限產品之應用面（例如食品、醫療等級之應用侷限） 、且在殘留觸媒之去活化程序中亦會產生廢酸（鹼）、及廢灰等，需進一步燃燒處理也會衍生環境汙染問題。此外，全球各煉油石化廠碳二至碳四（C2～C4）之生產反應器型態皆為填充床（Fixed-bed）；然而液態觸媒反應受限於批次反應器（Batch）、或連續式攪拌反應器（Continuous stirred tank reactor, CSTR）之生產方式，如商業技術AlphaButol即為CSTR反應方式，其丁烯產量規模不大，約708,000 噸/年（tons/year），這也是近年來陸續有學者們致力於固態觸媒催化乙烯寡聚研究之主要原因之一。 因此，固態觸媒在石化工業上之應用要比液態觸媒更受推崇、更廣泛、且更為實用，其大多為固態酸或載體型態之催化劑，具有下列多項優點：(1) 固體酸不會腐蝕反應器與管線，產業實際應用價值高、(2) 反應物及產物容易與固態觸媒分離、(3) 觸媒可以再生重覆使用、(4) 處置廢固體酸比廢酸液、廢鹼液容易。因此，乙烯雙聚及寡聚技術朝固態酸與載體型催化劑之方向發展將是未來必然之趨勢。 而上述之固態酸催化劑又可分為分子篩型與非分子篩型兩種，與矽鋁催化劑相比，分子篩催化劑具有活性高、選擇性好、穩定性高及抗毒能力強等優點。而以固態觸媒催化低碳烯烴雙聚或寡聚之相關研究多採用非分子篩型催化劑，如氧化鋁、矽酸鋁等矽鋁載體，其中氧化矽/氧化鋁上擔載鎳是較為人知之乙烯、丙烯及丁烯二聚反應之活性催化劑，相關細節可參見專利—US4740645、及US4542251。 針對乙烯在酸性分子篩上吸附之理論計算已有不少報導，某些學者研究了低碳烯烴在分子篩上之雙聚與齊聚反應機制，相關研究細節可參見論文二（Guo Yu-Hua, Acta Phys. Chim. Sin.,(2010), 26, 2503-2509、及G. Spoto, J. Chem. Soc., Faraday Trans., (1994), 90, 2827、及F. Geobaldo, J. Chem. Soc., Faraday Trans., (1997), 93, 1243）。 雖然這些研究有利於瞭解長鏈烯烴分子之分裂機制、烷烴在分子篩中之擴散性能、以及烯烴在分子篩酸性中心上之吸附性能等，但這些皆僅止於理論分子簇模型計算，又或者多為碳五（C5+）、及碳六至碳九（C6～C9）甚至更長碳鏈之α-烯烴產物，相關細節可參專利—US4542251。實際以分子篩型觸媒應用於乙烯之雙聚與寡聚反應之實驗從而生成丙烯及丁烯等低碳烯產品之報導則幾乎沒有。故，ㄧ般習用者係無法符合使用者於實際使用時以分子篩載體型固態金屬觸媒，透過填充床反應方式，有效應用在中低壓催化乙烯寡聚製備較高值化之丙烯及丁烯產物之所需。Butadiene is one of the important basic raw materials of petrochemical industry. At present, the main source in the world is obtained by extractive distillation from C4 cut of light oil cracking. It can also be obtained through the commercial dehydrogenation process of butene or butane. The existing commercial dehydrogenation process technology of butene has become mature, such as the "OX-DTM process" dehydrogenation process of Philips (Phillips), and the "Oxo-DTM process" oxidative dehydrogenation process of Petro-Tex. . However, in recent years, due to the rise of other petrochemical energy sources and the development of shale gas, the global oil refining and petrochemical industries have had to think of a way out to respond to the market impact brought by the refining structure change. In the case of a large number of refinery cracking structures that favor light component feeds, the output of light products such as methane, ethane, propane, and ethylene may be oversupplied in the future. Relative propylene, butene, and butadiene The output of even the heavier benzene, toluene, and xylene petrochemical raw materials may be in short supply. In the future, market prices of propylene, butene, and butadiene may soar, while market prices of methane, ethane, propane, and ethylene will decline. In order to convert ethylene into other products with four carbons (or more), the methods of ethylene oligomerization and oligomerization have been extensively studied in the early stage. Its main role is to manufacture and produce linear α-olefins. Related details See Taiwan Patent-TW223053B. For example, the ethylene oligomerization reaction to produce alpha-olefins now includes AlphaSelect technology developed by the French Petroleum Institute (IFP), and related production technologies such as Gulf Petroleum and Shell. The ethylene dimerization method belongs to the category of ethylene oligomerization, and its main purpose is to produce butene and hexene. Among them, IFP / Axens's AlphaButol technology and AlphaHexol technology are more famous, and AlphaButol is currently the only technology in the world that has commercially used ethylene polymerization to produce butene. From the perspective of reaction kinetics and transport phenomena, theoretically, homogeneous catalytic reactions are better than heterogeneous catalytic reactions, which means that liquid catalysts have better catalytic performance than solid catalysts. In terms of ethylene dimerization, IFP AlphaButol's patent US20140088331A1 used its liquid catalyst to compare the solid catalyst in Mitsui Chemicals Co., Ltd. JP2011 / 148720 with its liquid catalyst to catalyze ethylene dimerization and the ethylene conversion rate. 70% to 90%, butene yield of the target product is best 91%; the best example of solid catalyst in JP2011 / 148720 is 49.5% ethylene conversion, 79.4% butene selectivity, 39.3% yield . Other liquid catalyst research, such as the patent of Phillips Company, the liquid phase reaction in US4528415A is performed with nickel catalyst under the condition of adding acidic materials such as phosphine, and the selectivity of butene can reach 81-98% (carbon four fraction 1-butene). In addition, in recent years, solid-state catalyst-catalyzed ethylene oligomerization technology has also been actively developed. For example, Bi YL and others have prepared La / Ba / Sm oxide catalysts by ceramic synthesis. Carbon dioxide (CO 2 at 450-600 ° C ) ) Oxidative dehydrogenation in an atmosphere with a selectivity of 80% and an isobutylene yield of 22% can be found in the paper 1 (Bi YL, Catal. Today, (2000), 61, 369-375). Patent US7847140B2 is simulated by using NiSO 4 / SiO 2 -Al 2 O 3 (ALON) carrier catalyst and catalyzed distillation (Catalic distillation) technology. The best ethylene conversion rate is 96.8%, 1-butene and 1-hexane The olefin selectivity was 60% and 40%, respectively. However, from the perspective of industrial utilization, the liquid phase catalyst reaction method of the existing commercial technology still has the problem of subsequent separation procedures, and the solvent and by-products must be separated and removed from the product; and the liquid catalyst reaction Mostly use boron fluoride, aluminum chloride and alkyl aluminum compounds (such as aluminum triethyl (TEA), tributyl aluminum), or alkyl titanium compounds (such as tetrabutyl titanate (TBT)) ), Etc. as catalysts, please refer to patents-US20140088331A1, US4532370A, and US4615998A. The above-mentioned catalysts have hidden safety concerns about combustion and explosion. In addition, the metal components of the liquid catalyst remaining in the product may limit the application of the product (such as food, medical grade applications), and waste acid (alkali) and waste will be generated during the deactivation process of the residual catalyst. Ash, etc., need further combustion treatment will also cause environmental pollution problems. In addition, the types of production reactors for carbon two to carbon four (C2 to C4) in various refineries and petrochemical plants around the world are fixed-beds; however, the liquid catalyst reaction is limited to batch reactors, or Continuous stirring tank reactor (CSTR) production method, such as commercial technology AlphaButol is the CSTR reaction method, but its butene production scale is not large, about 708,000 tons per year (tons / year), which is also in recent years One of the main reasons why scholars have devoted themselves to the research of solid catalyst catalyzed ethylene oligomerization. Therefore, the application of solid catalysts in the petrochemical industry is more respected, more extensive, and more practical than liquid catalysts. Most of them are solid acid or carrier-type catalysts, which have the following advantages: (1) solid acid Does not corrode reactors and pipelines, has high industrial application value, (2) reactants and products are easily separated from solid catalysts, (3) catalysts can be reused and reused, (4) dispose of waste solid acid than waste acid liquid 2. Waste lye is easy. Therefore, the development of ethylene dimerization and oligomerization technology towards solid acid and supported catalysts will be an inevitable trend in the future. The above-mentioned solid acid catalysts can be divided into two types: molecular sieve type and non-molecular sieve type. Compared with silicon aluminum catalysts, molecular sieve catalysts have the advantages of high activity, good selectivity, high stability, and strong anti-toxicity. In the related studies on the catalysis of dimerization or oligomerization of low-carbon olefins with solid catalysts, non-molecular sieve type catalysts such as alumina and aluminosilicate are used. Among them, nickel is supported on silica / alumina. An active catalyst for the dimerization of ethylene, propylene and butene. For details, please refer to US Pat. No. 4,740,645 and US 4,452,251. There have been many reports on theoretical calculations of ethylene adsorption on acidic molecular sieves. Some scholars have studied the dimerization and oligomerization mechanism of low-carbon olefins on molecular sieves. For details of related research, please refer to the paper (Guo Yu-Hua, Acta). Phys. Chim. Sin., (2010), 26, 2503-2509, and G. Spoto, J. Chem. Soc., Faraday Trans., (1994), 90, 2827, and F. Geobaldo, J. Chem. Soc., Faraday Trans., (1997), 93, 1243). Although these studies are helpful for understanding the splitting mechanism of long-chain olefin molecules, the diffusion properties of alkanes in molecular sieves, and the adsorption properties of olefins on the acidic centers of molecular sieves, etc., these are only limited to theoretical molecular cluster model calculations, or they are mostly C5 +, C6-C9 and even longer carbon chain α-olefin products. For details, please refer to US Pat. No. 4,425,251. In fact, there have been few reports on the application of molecular sieve catalysts to the experiments of dimerization and oligomerization of ethylene to produce lower olefin products such as propylene and butene. Therefore, ordinary users are unable to meet the needs of users in the actual use of molecular sieve carrier-type solid metal catalysts, through the packed bed reaction method, effectively used in low-pressure catalytic oligomerization of ethylene to produce higher value propylene and butene products Needed.
請參閱『第１圖及第２圖』所示，係分別為本發明酸性金屬分子篩載體觸媒進行催化乙烯寡聚之流程示意圖、及本發明酸性金屬分子篩載體觸媒之製備流程示意圖。如圖所示：本發明係一種有機酸飾分子篩低壓催化乙烯寡聚同時產丙烯及丁烯之方法，係包括催化乙烯寡聚反應之操作條件，以及所使用觸媒之組成分配方與製備方法，主要以環烷酸金屬鹽為前驅物配方所製備之高矽鋁比分子篩型金屬固態酸觸媒，採用不含硫酸（鹽）、氯（鹽）、氯酸（鹽）、及過氯酸（鹽）之腐蝕性鹽類成份之配方，不會腐蝕反應器、管線與設備者。 進一步詳細說明，本發明係以酸性金屬分子篩載體觸媒低壓催化乙烯寡聚、轉化製備生成丙烯及丁烯之方法。本發明係利用含浸法來合成出該酸性金屬分子篩載體觸媒，從而改變載體之酸性及活性，使其適用於乙烯寡聚同時生產丙烯及丁烯之轉化反應。由下列實施例之結果顯示含浸合成後之酸性金屬分子篩載體觸媒具備高乙烯轉化率，且生成丙烯及丁烯具有不錯之選擇性。酸中心通常係由分子篩所提供，而分子篩由於其合適之酸性質及特殊之孔道結構而具有高度之選擇性。 本發明之觸媒係以一種高矽鋁比分子篩飾載體粉、或顆粒、或柱狀作為擔體基質（matrix），如步驟s10；經直接或共同含浸於本發明配方環烷酸金屬鹽、及苯、或甲苯、或正己烷、或上述混合物等助試劑，再予以高溫煅燒生成熱穩定性高之酸性金屬分子篩載體觸媒，如步驟s11。本發明之酸性金屬分子篩載體觸媒製備一般步驟如下： 步驟s111：秤取適量之環烷酸金屬鹽，加入苯、甲苯、正己烷、或其混合物等助試劑中，使環烷酸金屬鹽與助試劑重量之比例介於0.001～1之間，再將25g之高矽鋁比分子篩飾載體加入上述20ml溶液中進行含浸。 步驟s112：含浸後之觸媒經12～24小時之乾燥後再進行煅燒，煅燒程序係在200～700°C間之空氣氛圍下經2～12小時完成。 步驟s113：煅燒後之觸媒以氫氣、或氫氣/氬氣、或氫氣/氮氣混合氣在200～700°C間進行活化處理，活化時間為2～12小時。 步驟s114：活化後之觸媒經阻絕空氣冷卻至室溫即得所需之觸媒，即形成一熱穩定性高之酸性金屬分子篩載體觸媒。以下該等製備例或實施例皆是在常壓且充滿乾燥氮氣、氦氣、或氬氣之環境下實施。其 本發明之酸性金屬分子篩載體觸媒係屬於可再生性觸媒，該觸媒之再生須以空氣或含有氧氣之混合氣體在溫度200～700°C間連續操作完成。再生時間為4～12小時可確保回復觸媒之活性與選擇性，惟觸媒再生及週期壽命評估不在本案探討範圍之內。 本發明之酸性金屬分子篩載體觸媒能應用在低壓催化乙烯所進行之寡聚反應上，所使用之進料物流可以是高純度化學級之乙烯，也可以是工業級、或者是其惰性氣體稀釋物流，使用本發明酸性金屬分子篩載體觸媒所進行寡聚反應之乙烯物流至少含有重量百分比在10～99.8 %之間。 以本發明酸性金屬分子篩載體觸媒進行催化乙烯寡聚之反應裝置及實驗方法敘述如下。如步驟s12，將本發明酸性金屬分子篩載體觸媒裝填入一固定床反應器（如不銹鋼管狀反應器）中，除了觸媒床段以外，其觸媒床上下端皆以耐高溫惰性固體顆粒裝填、支撐。此惰性固體顆粒可為耐高溫玻璃珠、或氧化鋁墊球，其另一重要作用係使進料反應物流動分布更均勻，不致產生隙流效應（channeling effect）。 低壓催化寡聚反應發生之同時，亦可能有其他烷類副產物生成，為避免過多非所欲之副產物及結焦（coke）產生，而降低了對丙烯及丁烯之選擇性，於是，就本發明內容之步驟s13中之反應溫度，係限定在不超過500°C；於本發明具體實施例中所示範者，步驟s13中之最佳反應溫度係設定在380～450°C之間。如是，藉由上述揭露之流程構成一全新之有機酸飾分子篩低壓催化乙烯寡聚同時產丙烯及丁烯之方法。＜ 乙烯轉化率與丙烯或丁烯之選擇性之評估方式 ＞
本發明之乙烯寡聚反應操作特色係控制在氣相反應中進行，進行中至反應完成之任意時間點採樣皆為氣態產物，以採氣袋將該氣態產物樣品取出，並藉由一煉油氣體分析儀（AC Hi-Speed RGA）來評估反應起始物（即乙烯）之轉化率（意指被反應掉之比率），以及丙烯、及丁烯之選擇性（意指佔所有產物的比率）。反應之操作變數包含壓力、溫度、進料組成、及重量空間流速（WHSV）等。其中AC Hi-Speed RGA係屬於氣相層析儀，型號為RGA Hi-Speed System Agilent 7890 GC；分析管柱為毛細管型式，偵測器為火焰離子化偵測器（Flame Ionization Detector, FID）與熱導偵測器（Thermal Conductivity Detector, TCD）之雙偵測器同步使用。 本發明另以下列敘述性而非限制性之例子來進一步加以闡述。以下將以實施例進一步說明本發明，惟該等實施例僅為例示說明之用，而非用以限制本發明。＜ 製備例 ＞ 分子篩載體 金屬固態酸之製備
依照上述酸性金屬分子篩載體觸媒製備方法，一個較佳之例子說明如下：秤取環烷酸鎳，加入甲苯溶劑中配製成重量百分濃度為0.4～20 %之鎳金屬試劑，取0.1～5.0 g不等之該試劑以正己烷混合稀釋為20 ml之含浸液，再將25 g之高矽鋁比分子篩飾載體混合物含浸於上述20 ml之溶液中30°C約12小時。再於排氣櫃乾燥約12小時後取出進行煅燒，煅燒係在200～700°C之空氣或氮氣氛圍下進行12小時完成，並冷卻至室溫即得實驗所需之未活化觸媒。活化觸媒係再以純氫氣或5 %氫氣在500°C下進行活化處理，活化時間為6小時，即得實驗所需之活化觸媒-酸性金屬分子篩載體觸媒。此觸媒成份分別為含有0.01～10重量%之鎳金屬及鎳氧化物附載於90～99.99重量%之高矽鋁比分子篩飾載體上（或內）之有機酸性金屬分子篩載體觸媒（本實施例中以Ni-Z(ZSM-5型載體)簡稱之、及比較例以Ni-F(FCC載體)簡稱之）。＜ 實施例 ＞ 催化乙烯寡聚生產丙烯及丁烯
＜實施例1＞ 依照上述實驗方法，一個較佳之例子，催化乙烯寡聚生產丙烯、及丁烯反應，說明如下：以純度在99.8之乙烯及99.99之氮氣作為進料，使用如製備例中4 g之未活化之Ni-Z觸媒來進行反應。操作條件固定為壓力1.5 kg/cm2
，溫度450°C，反應結果示於表一中。反應初期乙烯之轉化率達97.9 %以上（未標於表一中），初期以C1～C4烷類居多，此乃過渡反應之中間物；然反應15分鐘（min）後，目標產物丙烯及丁烯快速生成（烷類衰減），5～6小時後丙烯及丁烯產量達最高且穩定生成。當反應達6小時，乙烯在C2中之比例高達90.39 %、丙烯在C3中之比例高達94.80 %、丁烯在C4中之比例高達93.36 %，系統中烯烴產物所占比例極高。就整體反應（真實選擇率及產率）而言，6小時後乙烯之轉化率至少維持在62.7 %以上，最終目標產物丙烯、及丁烯之選擇率分別為26.2 %、及29.4 %，總和為55.6 %（以乙烯計）；其產率分別為16.4 %、及18.4 %，總和達34.9 %（以乙烯計）。 對照專利JP2011/148720固態觸媒催化技術，其反應機制有兩步，然而其第二步其實是單烯類再進行氧化脫氫轉化為丁二烯，真正產單烯類（丁烯）之反應是其第一步，在150～400°C下之反應，其最佳實施例之乙烯轉化率為49.5 %、目標產物丁烯之選擇率為79.4 %、產率為39.3 %。然而，在同樣以生產低碳單烯類（非再進行氧化脫氫轉化為二烯類）為目標之比較基準上，以本實施例1與專利JP2011/148720最佳例子進行比較，本實施例1之主要優勢為低壓下反應，雖然單烯類之選擇率較低（55.6 %），但轉化率較高（62.7 %），單烯類總產率結果相近；此外，本發明之另一特點為產物組成乃同時生成相近似產量之丙烯及丁烯，此點與所有先前技術截然不同，未來在生產應用層面上之彈性更廣。 ＜實施例2＞ 以與實施例1 相同之方式催化乙烯寡聚反應，而將觸媒更改為經活化處理後之Ni-Z載體觸媒，其它操作條件不變，反應結果示於表一中。反應初期乙烯之轉化率高達97.1 %，初期產物C1～C4烷類居多，此乃整體反應之中間物；然反應15 min後，目標產物丙烯及丁烯快速生成，5～6小時後丙烯及丁烯產量達最高且穩定生成。當反應達6小時，乙烯在C2中之比例高達85.67 %、丙烯在C3中之比例高達89.62 %、丁烯在C4中之比例高達86.69 %，系統中幾乎仍以烯烴產物為主導。就整體反應（真實選擇率及產率）而言，6小時後乙烯之轉化率可維持在72.7 %以上，最終目標產物丙烯、及丁烯之選擇率分別為23.9 %、及27.7 %，總和為51.5 %（以乙烯計）；其產率分別為17.4 %、及20.1 %，總和達37.5 %（以乙烯計）。然而實施例2之結果相較於實施例1，結果表明經活化處理後之觸媒活性可被提高，由6小時之乙烯轉化率可以觀察，但同時也因活化處理過之催化劑活性較高，亦同時提高副反應之進行，因此導致丙烯及丁烯之選擇率稍微降低，然而整體產率係比實施例1略佳。 對照專利JP2011/148720固態觸媒催化技術，其反應機制有兩步，然而其第二步其實是單烯類再進行氧化脫氫轉化為丁二烯，真正產單烯類（丁烯）之反應是其第一步，在150～400°C下之反應，其最佳實施例之乙烯轉化率為49.5 %、目標產物丁烯之選擇率為79.4 %、產率為39.3 %。然而，在同樣以生產低碳單烯類（非再進行氧化脫氫轉化為二烯類）為目標之比較基準上，以本實施例2與專利JP2011/148720最佳例子進行比較，本實施例2之主要優勢為低壓下反應，雖然單烯類之選擇率較低（51.5 %），但轉化率較高（72.7 %），單烯類總產率結果相近；此外，本發明之另一特點為產物組成乃同時生成相近似產量之丙烯及丁烯，此點與所有先前技術截然不同，未來在生產應用層面上之彈性更廣。 ＜實施例3＞ 以與實施例1 相同之方式催化乙烯寡聚反應，而將反應溫度更改為380°C，其它操作條件不變，反應結果示於表一中。反應初期乙烯之轉化率高達95.5 %，初期產物C1～C4烷類居多，此乃整體反應之中間物；然反應15 min後，目標產物丙烯及丁烯快速生成，5～6小時後丙烯及丁烯產量達最高且穩定生成。當反應達6小時，乙烯在C2中之比例為99.36 %、且丙烯在C3中之比例高達100 %、丁烯在C4中之比例高達100 %，產物幾乎為丙烯及丁烯，沒有丙烷及丁烷。雖然丙烯及丁烯之選擇率高，但反應6小時乙烯轉化率僅剩15.6 %，殘留量達乙烯進料之84.4 %，結果顯示該條件下催化乙烯之反應性差，就算丙烯及丁烯之選擇率高，但其整體生成產率卻偏低。就整體反應（真實選擇率及產率）而言，6小時後最終目標產物丙烯、及丁烯之選擇率分別為15.0 %、及29.1 %，總和為44.1 %（以乙烯計）；其產率分別為2.3 %、及4.5 %，總和僅6.9 %（以乙烯計）。 ＜實施例4＞ 以與實施例1 相同之方式催化乙烯寡聚反應，而將觸媒更改為經活化處理後之Ni-Z載體觸媒，並將反應溫度更改為380°C，其它操作條件不變，反應結果示於表一中。反應初期乙烯之轉化率高達96.7 %，初期產物C1～C4烷類居多，此乃整體反應之中間物；然反應15 min後，目標產物丙烯及丁烯快速生成，5～6小時後丙烯及丁烯產量達最高且穩定生成。當反應達6小時，乙烯在C2中之比例為98.82 %、且丙烯在C3中之比例高達100 %、丁烯在C4中之比例高達96.63 %，產物幾乎為丙烯及丁烯。雖然丙烯及丁烯之選擇率高，但反應6小時乙烯轉化率僅剩21.6 %，殘留量達乙烯進料之78.4 %，結果顯示該條件下催化乙烯之反應性差，就算丙烯及丁烯之選擇率高，但其整體生成產率卻偏低。就整體反應（真實選擇率及產率）而言，6小時後最終目標產物丙烯、及丁烯之選擇率分別為17.0 %、及28.6 %，總和為45.6 %（以乙烯計）；其產率分別為3.7 %、及6.2 %，總和僅9.8 %（以乙烯計）。 然而實施例4之結果較實施例3略佳，結果表明經活化處理後之觸媒活性可被提高，使其在較差之催化條件下仍具有一定程度之效果，但效果並不顯著，且尚須考慮活化處理所需之能耗及成本問題。 ＜實施例5＞ 以與實施例1 相同之方式催化乙烯寡聚反應，而將反應溫度更改為310°C，其它操作條件不變，反應結果示於表一中。反應初期乙烯之轉化率高達95.2 %，初期產物C1～C4烷類居多，此乃整體反應之中間物；然反應15 min後，目標產物丙烯及丁烯快速生成，5～6小時後丙烯及丁烯產量達最高且穩定生成。當反應達6小時，乙烯在C2中之比例為100 %、且丙烯在C3中之比例高達100 %、丁烯在C4中之比例高達100 %，產物幾乎為丙烯及丁烯。雖然丙烯及丁烯之選擇率高，但反應6小時乙烯轉化率僅剩5.8 %，殘留量達乙烯進料之94.2 %，結果表明該條件下催化乙烯之反應性極差，幾乎沒什麼反應性。 ＜實施例6＞ 以與實施例1 相同之方式催化乙烯寡聚反應，而將觸媒更改為經活化處理後之Ni-Z載體觸媒，並將反應溫度更改為310°C，其它操作條件不變，反應結果示於表一中。反應初期乙烯之轉化率高達94.5 %，初期產物C1～C4烷類居多，此乃整體反應之中間物；然反應15 min後，目標產物丙烯及丁烯快速生成，5～6小時後丙烯及丁烯產量達最高且穩定生成。當反應達6小時，乙烯在C2中之比例為99.85 %、且丙烯在C3中之比例高達100 %、丁烯在C4中之比例高達100 %，產物幾乎為丙烯及丁烯。雖然丙烯及丁烯之選擇率高，但反應6小時乙烯轉化率僅剩6.9 %，殘留量達乙烯進料之93.1 %，結果表明該條件下催化乙烯之反應性極差，幾乎沒什麼反應性。 然而不同於實施例3及4，實施例5及6中乙烯大量殘留、幾乎無反應性，結果表明雖然可透過活化處理來提高觸媒活性，但在此相對較低溫度下明顯不利於催化反應之進行，整體而言，反應最終僅生成極其微量之丙烯與丁烯。 ＜比較例1＞ 以與製備例相同之方式製備有機酸性載體觸媒，除了將原來之ZSM-5型高矽鋁比分子篩飾載體配方改以FCC載體粉取代之，其餘皆同。並施以與實施例1 相同之方式催化乙烯寡聚反應，唯觸媒有經過活化處理，其它操作條件不變，反應結果示於表一中。 結果顯示，該類型載體觸媒對烯烴產物之選擇性很高，產物組成中幾乎沒有烷類，但觸媒對乙烯之反應性極差，幾乎沒什麼反應性。反應6小時之丙烯及丁烯產率與實施例5及6結果相仿。 ＜比較例2＞ 以與製備例相同之方式製備有機酸性載體觸媒，除了將原來之ZSM-5型高矽鋁比分子篩飾載體配方改以FCC載體粉取代之，其餘皆同。並施以與實施例1 相同之方式催化乙烯寡聚反應，唯觸媒有經過活化處理，並將反應溫度更改為380°C，其它操作條件不變，反應結果示於表一中。 結果顯示，該類型載體觸媒對烯烴產物之選擇性很高，產物組成中幾乎沒有烷類，但觸媒對乙烯之反應性極差，幾乎沒什麼反應性。反應6小時之丙烯及丁烯產率與實施例5及6結果相仿。 ＜比較例3＞ 以與製備例相同的方式製備有機酸性載體觸媒，除了將原來之ZSM-5型高矽鋁比分子篩飾載體配方改以FCC載體粉取代之，其餘皆同。並施以與實施例1 相同之方式催化乙烯寡聚反應，唯觸媒有經過活化處理，並將反應溫度更改為310°C，其它操作條件不變，反應結果示於表一中。 表一結果顯示，該類型載體觸媒對烯烴產物之選擇性很高，產物組成中幾乎沒有烷類，但觸媒對乙烯之反應性極差，幾乎沒什麼反應性。反應6小時之丙烯及丁烯產率與實施例5及6結果相仿。 本發明觸媒之另一特點係除中壓（35 kg/cm2
）條件下可實施，其可降低到1.0～3.0 kg/cm2
之低壓條件下反應，該催化程序操作安全，可避免液態觸媒催化反應系統如商業技術AlphaButol須在中壓（≥35 kg/cm2
）甚至高壓條件下操作之侷限，本發明所提低壓固態觸媒催化技術除了安全性高之外，與其他分離程序、純化單元之結合性也相對較高。 且本發明催化技術之產品中同時包含丙烯及丁烯，且丙烯及丁烯產量相近，此產物組成有別於先前技術中一般乙烯雙聚之催化結果，此可作為乙烯雙聚或寡聚轉化為丁烯以外之其他高值化產品之另一種新之生產方法。 藉此，本發明之目的在於避免目前商業技術液相反應直接採用液態觸媒（氯化鋁、烷基鋁化物、以及烷基鈦化物等）催化乙烯生產丁烯及己烯等所衍生之缺點。不僅消除液態觸媒操作不慎有燃燒、爆炸之安全疑慮，並避免反應之末端可能產生廢酸、廢鹼、及廢灰之汙染問題，同時，本發明之有機酸性金屬分子篩載體觸媒採用不含硫酸（鹽）、氯（鹽）、氯酸（鹽）、及過氯酸（鹽）等腐蝕性鹽類成份之配方，不會腐蝕反應器、管線與設備，透過填充床反應方式，可有效應用在中低壓催化乙烯寡聚製備較高值化之丙烯及丁烯產物，亦可再生重覆使用、簡化製程之分離程序，達到降低操作設備之投資成本。 綜上所述，本發明係一種有機酸飾分子篩低壓催化乙烯寡聚同時產丙烯及丁烯之方法，可有效改善習用之種種缺點，為高矽鋁比分子篩飾載體之環烷酸金屬觸媒催化乙烯寡聚同時製備丙烯及丁烯之方法，主要係降低烷類副產物、並提高低碳烯（丙烯及丁烯）之選擇性，以獲得較多之丙烯及丁烯產物，進而使本發明之産生能更進步、更實用、更符合使用者之所須，確已符合發明專利申請之要件，爰依法提出專利申請。 惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍；故，凡依本發明申請專利範圍及發明說明書內容所作之簡單的等效變化與修飾，皆應仍屬本發明專利涵蓋之範圍內。Please refer to "Figures 1 and 2", which are schematic diagrams of the process for catalyzing the oligomerization of ethylene by the acid metal molecular sieve carrier catalyst of the present invention, and the preparation process of the acid metal molecular sieve carrier catalyst of the present invention. As shown in the figure, the present invention is a method for producing propylene and butene at the same time by low pressure catalyzing ethylene oligomerization with organic acid decorated molecular sieves. It includes operating conditions for catalyzing ethylene oligomerization, and composition distribution method and preparation method of the catalyst used. High molecular weight sieve type metal solid acid catalyst prepared with naphthenic acid metal salt as the precursor, using sulfuric acid (salt), chlorine (salt), chloric acid (salt), and perchloric acid. (Salt) Corrosive salt formulations will not corrode reactors, pipelines and equipment. In further detail, the present invention is a method for preparing propylene and butene by catalyzing the oligomerization and conversion of ethylene with an acid metal molecular sieve carrier catalyst under low pressure. The invention uses the impregnation method to synthesize the acid metal molecular sieve carrier catalyst, thereby changing the acidity and activity of the carrier, making it suitable for the conversion reaction of ethylene oligomerization and simultaneous production of propylene and butene. The results of the following examples show that the acidic metal molecular sieve carrier catalyst after impregnation synthesis has a high ethylene conversion rate and good selectivity to propylene and butene. Acid centers are usually provided by molecular sieves, and molecular sieves are highly selective due to their suitable acid properties and special pore structure. The catalyst of the present invention uses a high silicon-aluminum ratio molecular sieve carrier powder, or granules, or a columnar shape as a support matrix (step s10); by directly or jointly impregnating the metal naphthenate salt of the formula of the present invention And auxiliary reagents such as benzene, toluene, n-hexane, or the above mixture, and then calcined at high temperature to form an acid metal molecular sieve carrier catalyst with high thermal stability, as in step s11. The general steps for preparing an acidic metal molecular sieve carrier catalyst according to the present invention are as follows: Step s111: Weigh an appropriate amount of metal naphthenate and add it to auxiliary agents such as benzene, toluene, n-hexane, or a mixture thereof, so that the metal The weight ratio of the auxiliary reagent is between 0.001 and 1, and 25 g of the high-silicon-aluminum-ratio molecular sieve carrier is added to the above 20 ml solution for impregnation. Step s112: The impregnated catalyst is dried for 12 to 24 hours and then calcined. The calcination process is completed in an air atmosphere at 200 to 700 ° C in 2 to 12 hours. Step s113: The calcined catalyst is activated by hydrogen, or hydrogen / argon, or a hydrogen / nitrogen mixed gas at 200-700 ° C, and the activation time is 2-12 hours. Step s114: The activated catalyst is cooled to room temperature by blocking the air to obtain the required catalyst, that is, an acid metal molecular sieve carrier catalyst with high thermal stability is formed. The following preparations or examples are carried out under an atmosphere of normal pressure and filled with dry nitrogen, helium, or argon. The acidic metal molecular sieve carrier catalyst of the present invention belongs to a renewable catalyst. The regeneration of the catalyst must be completed by continuous operation of air or a mixed gas containing oxygen at a temperature of 200 to 700 ° C. The regeneration time is 4-12 hours to ensure the recovery of the catalyst's activity and selectivity, but the catalyst regeneration and cycle life assessment are beyond the scope of this case. The acid metal molecular sieve carrier catalyst of the present invention can be applied to the oligomerization reaction of low-pressure catalytic ethylene. The feed stream used can be high-purity chemical-grade ethylene, or industrial-grade, or its inert gas dilution. Stream, the ethylene stream using the acid metal molecular sieve carrier catalyst of the present invention for oligomerization contains at least 10-99.8% by weight. A reaction device and an experimental method for catalyzing ethylene oligomerization by using the acid metal molecular sieve carrier catalyst of the present invention are described below. In step s12, the acidic metal molecular sieve carrier catalyst of the present invention is charged into a fixed bed reactor (such as a stainless steel tubular reactor). Except for the catalyst bed section, the lower end of the catalyst bed is filled with high temperature resistant inert solid particles. ,support. The inert solid particles can be high-temperature resistant glass beads or alumina bead balls. Another important function is to make the flow of the reactants in the feed material more uniform and not cause a channeling effect. At the same time that the low-pressure catalytic oligomerization reaction occurs, other alkane by-products may also be formed. In order to avoid excessive undesired by-products and coke production, and reduce the selectivity to propylene and butene, therefore, The reaction temperature in step s13 of the present invention is limited to not more than 500 ° C. As exemplified in the specific embodiment of the present invention, the optimal reaction temperature in step s13 is set between 380-450 ° C. If so, the method disclosed above constitutes a new method for low-pressure catalytic oligomerization of ethylene to produce propylene and butene through organic acid- decorated molecular sieves. < Evaluation Method of Ethylene Conversion Rate and Selectivity of Propylene or Butene > The ethylene oligomerization operation feature of the present invention is controlled in a gas phase reaction, and samples are taken as gaseous products at any time point from the progress to the completion of the reaction. A gas extraction bag was used to extract the gaseous product sample, and the conversion rate of the reaction starting material (ie, ethylene) (meaning the rate of reaction), and propylene were evaluated by an oil refinery gas analyzer (AC Hi-Speed RGA). , And the selectivity of butene (meaning the ratio of all products). The operating variables of the reaction include pressure, temperature, feed composition, and weight space flow rate (WHSV). Among them, AC Hi-Speed RGA is a gas chromatograph, the model is RGA Hi-Speed System Agilent 7890 GC; the analytical column is capillary type, and the detector is Flame Ionization Detector (FID) and Thermal Conductivity Detector (TCD) dual detectors are used simultaneously. The invention is further illustrated by the following descriptive rather than limiting examples. Hereinafter, the present invention will be further described by examples, but these examples are only for illustration and not to limit the present invention. < Preparation example > Preparation of molecular sieve carrier metal solid acid According to the above-mentioned acid metal molecular sieve carrier catalyst preparation method, a preferred example is explained as follows: nickel naphthenate is weighed out and added to the toluene solvent to prepare a concentration of 0.4% by weight 20% nickel metal reagent, take 0.1 ～ 5.0 g of this reagent and dilute it with n-hexane to 20 ml of impregnating solution, and then impregnate 25 g of high silicon-aluminum ratio molecular sieve carrier mixture into the above 20 ml solution 30 ° C for about 12 hours. After drying in the exhaust cabinet for about 12 hours, it is taken out for calcination. The calcination is completed in an air or nitrogen atmosphere at 200-700 ° C for 12 hours and cooled to room temperature to obtain the unactivated catalyst required for the experiment. The activation catalyst is then treated with pure hydrogen or 5% hydrogen at 500 ° C. The activation time is 6 hours to obtain the activated catalyst-acid metal molecular sieve carrier catalyst required for the experiment. This catalyst component is an organic acidic metal molecular sieve carrier catalyst containing 0.01 to 10% by weight of nickel metal and nickel oxide supported on (or inside) a high silica-to-aluminum molecular sieve decoration carrier (or inside) (this implementation In the examples, Ni-Z (ZSM-5 type carrier) is abbreviated, and in Comparative Examples, Ni-F (FCC carrier) is abbreviated). < Example > Catalyzing oligomerization of ethylene to produce propylene and butene <Example 1> According to the above experimental method, a preferred example is to catalyze the reaction of ethylene oligomerization to produce propylene and butene, as follows: Nitrogen gas of 99.99 was used as a feed, and the reaction was performed using 4 g of an unactivated Ni-Z catalyst as in the preparation example. The operating conditions were fixed at a pressure of 1.5 kg / cm 2 and a temperature of 450 ° C. The reaction results are shown in Table 1. The conversion rate of ethylene reached 97.9% at the beginning of the reaction (not shown in Table 1). Most of C1 to C4 alkanes were used in the initial stage. This is the intermediate of the transition reaction. After 15 minutes (min), the target products propylene and butyl Ethylene is rapidly produced (decanes are decayed). After 5 to 6 hours, the production of propylene and butene reaches the highest and is stable. When the reaction reaches 6 hours, the proportion of ethylene in C2 is as high as 90.39%, the proportion of propylene in C3 is as high as 94.80%, and the proportion of butene in C4 is as high as 93.36%. The proportion of olefin products in the system is extremely high. In terms of the overall reaction (true selectivity and yield), the conversion of ethylene remained at least 62.7% after 6 hours. The final target product propylene and butene selectivity were 26.2% and 29.4%, respectively. 55.6% (based on ethylene); the yields were 16.4% and 18.4%, respectively, and the total amount reached 34.9% (based on ethylene). Compared with the patent JP2011 / 148720 solid catalyst catalytic technology, the reaction mechanism has two steps. However, the second step is actually the reaction of olefins to undergo oxidative dehydrogenation to convert to butadiene, and the reaction of truly producing monoenes (butenes) It is the first step of the reaction at 150-400 ° C. In the best embodiment, the ethylene conversion is 49.5%, the selectivity of the target product butene is 79.4%, and the yield is 39.3%. However, on the basis of comparison, which is also aimed at the production of low-carbon monoenes (non-re-oxidative dehydrogenation to diene), this embodiment is compared with the best example of patent JP2011 / 148720. This embodiment The main advantage of 1 is the reaction under low pressure. Although the selectivity of monoenes is low (55.6%), the conversion rate is high (62.7%), and the overall yield of monoenes is similar; in addition, another feature of the present invention For the product composition, propylene and butene are produced simultaneously with similar yields. This is completely different from all previous technologies, and it will have greater flexibility in terms of production and application in the future. 〈Example 2〉 In the same manner as in Example 1, the catalyst was catalyzed by ethylene oligomerization, and the catalyst was changed to a Ni-Z carrier catalyst after activation treatment. Other operating conditions remained unchanged. The reaction results are shown in Table 1. . The conversion rate of ethylene in the initial stage of the reaction was as high as 97.1%, and most of the initial products C1 to C4 alkanes were intermediates of the overall reaction. However, after 15 minutes of reaction, the target products propylene and butene were rapidly formed. After 5 to 6 hours, the propylene and butene were rapidly formed. The highest ene production and stable production. When the reaction reaches 6 hours, the proportion of ethylene in C2 is as high as 85.67%, the proportion of propylene in C3 is as high as 89.62%, and the proportion of butene in C4 is as high as 86.69%. The system is still dominated by olefin products. In terms of the overall reaction (true selectivity and yield), after 6 hours, the ethylene conversion rate can be maintained above 72.7%, and the final target product propylene and butene selection rates are 23.9% and 27.7%, respectively. The total is 51.5% (based on ethylene); the yields were 17.4% and 20.1% respectively, and the total amount reached 37.5% (based on ethylene). However, the result of Example 2 is compared with that of Example 1. The results show that the catalyst activity can be improved after the activation treatment, and the ethylene conversion rate can be observed from 6 hours, but at the same time, the activation treatment has a higher activity. At the same time, the progress of the side reactions is also improved, so that the selectivity of propylene and butene is slightly reduced, but the overall yield is slightly better than that of Example 1. Compared with the patent JP2011 / 148720 solid catalyst catalytic technology, the reaction mechanism has two steps. However, the second step is actually the reaction of olefins to undergo oxidative dehydrogenation to convert to butadiene, and the reaction of truly producing monoenes (butene) It is the first step of the reaction at 150-400 ° C. In the best embodiment, the ethylene conversion is 49.5%, the selectivity of the target product butene is 79.4%, and the yield is 39.3%. However, on the basis of comparison, which also aims at producing low-carbon monoenes (non-reoxidative dehydrogenation to diene), this embodiment is compared with the best example of patent JP2011 / 148720. This embodiment The main advantage of 2 is the reaction under low pressure. Although the selectivity of monoenes is low (51.5%), the conversion rate is high (72.7%), and the overall yield of monoenes is similar; in addition, another feature of the present invention For the product composition, propylene and butene are produced simultaneously with similar yields. This is completely different from all previous technologies, and it will have greater flexibility in terms of production and application in the future. <Example 3> The ethylene oligomerization reaction was catalyzed in the same manner as in Example 1 except that the reaction temperature was changed to 380 ° C, and other operating conditions were not changed. The reaction results are shown in Table 1. In the initial stage of the reaction, the conversion rate of ethylene was as high as 95.5%, and most of the initial products C1 to C4 alkanes were intermediates of the overall reaction. However, after 15 minutes of reaction, the target products propylene and butene were rapidly formed. After 5 to 6 hours, the propylene and butene were rapidly formed. The highest ene production and stable production. When the reaction time is 6 hours, the proportion of ethylene in C2 is 99.36%, the proportion of propylene in C3 is up to 100%, and the proportion of butene in C4 is up to 100%. The product is almost propylene and butene, without propane and butene. alkyl. Although the selectivity of propylene and butene is high, only 15.6% of the ethylene conversion rate remains after 6 hours of reaction, and the residual amount reaches 84.4% of the ethylene feed. The results show that the catalytic reactivity of ethylene under this condition is poor, even if the choice of propylene and butene is poor. The yield is high, but the overall yield is low. In terms of the overall reaction (true selectivity and yield), the selectivity of the final target products propylene and butene after 6 hours is 15.0% and 29.1%, respectively, and the total is 44.1% (based on ethylene); its yield They are 2.3% and 4.5% respectively, and the total is only 6.9% (in terms of ethylene). 〈Example 4〉 In the same manner as in Example 1, the catalyst was catalyzed by ethylene oligomerization, and the catalyst was changed to an activated Ni-Z carrier catalyst, and the reaction temperature was changed to 380 ° C. Other operating conditions Intact, the reaction results are shown in Table 1. In the initial stage of the reaction, the conversion rate of ethylene was as high as 96.7%, and the initial products were C1 to C4 alkanes, which were intermediates of the overall reaction. However, after 15 minutes of reaction, the target products, propylene and butene, were rapidly formed. The highest ene production and stable production. When the reaction reaches 6 hours, the proportion of ethylene in C2 is 98.82%, the proportion of propylene in C3 is as high as 100%, and the proportion of butene in C4 is as high as 96.63%. The products are almost propylene and butene. Although the selectivity of propylene and butene is high, only 21.6% of the ethylene conversion remains after 6 hours of reaction, and the residual amount reaches 78.4% of the ethylene feed. The results show that the catalytic reactivity of ethylene under this condition is poor, even if the choice of propylene and butene is poor. The yield is high, but the overall yield is low. In terms of the overall reaction (true selectivity and yield), the selectivity of the final target products propylene and butene after 1 hour is 17.0% and 28.6%, respectively, and the total is 45.6% (based on ethylene); its yield They are 3.7% and 6.2% respectively, and the total is only 9.8% (in terms of ethylene). However, the result of Example 4 is slightly better than that of Example 3. The results show that the catalyst activity can be improved after the activation treatment, so that it still has a certain degree of effect under poor catalytic conditions, but the effect is not significant, and Consideration must be given to the energy consumption and cost of the activation process. <Example 5> The ethylene oligomerization reaction was catalyzed in the same manner as in Example 1 except that the reaction temperature was changed to 310 ° C, and other operating conditions were not changed. The reaction results are shown in Table 1. The conversion rate of ethylene in the initial stage of the reaction was as high as 95.2%, and most of the initial products C1 to C4 alkanes were intermediates of the overall reaction. However, after 15 minutes of reaction, the target products propylene and butene were rapidly formed. After 5 to 6 hours, the propylene and butene were rapidly formed. The highest ene production and stable production. When the reaction reaches 6 hours, the proportion of ethylene in C2 is 100%, the proportion of propylene in C3 is up to 100%, and the proportion of butene in C4 is up to 100%. The products are almost propylene and butene. Although the selectivity of propylene and butene is high, the ethylene conversion rate after 6 hours of reaction is only 5.8%, and the residual amount is 94.2% of the ethylene feed. The results show that the catalytic reactivity of ethylene under this condition is extremely poor, with little reactivity. 〈Example 6〉 In the same manner as in Example 1, the catalyst was catalyzed by ethylene oligomerization, and the catalyst was changed to an activated Ni-Z carrier catalyst, and the reaction temperature was changed to 310 ° C. Other operating conditions Intact, the reaction results are shown in Table 1. At the beginning of the reaction, the conversion rate of ethylene was as high as 94.5%, and most of the initial products were C1 to C4 alkanes, which were intermediates in the overall reaction. However, after 15 minutes of reaction, the target products, propylene and butene, were rapidly formed. After 5 to 6 hours, the propylene and butene were rapidly formed. The highest ene production and stable production. When the reaction reaches 6 hours, the proportion of ethylene in C2 is 99.85%, the proportion of propylene in C3 is as high as 100%, and the proportion of butene in C4 is as high as 100%. The products are almost propylene and butene. Although the selectivity of propylene and butene is high, only 6.9% of the ethylene conversion rate remains after 6 hours of reaction, and the residual amount reaches 93.1% of the ethylene feed. The results show that the catalytic reactivity of ethylene under this condition is extremely poor, with little reactivity. However, unlike Examples 3 and 4, ethylene in Examples 5 and 6 had a large amount of residual and almost no reactivity. The results show that although the catalytic activity can be improved through activation treatment, it is obviously not good for catalytic reactions at this relatively low temperature. As it progresses, the reaction ultimately produces only very small amounts of propylene and butene. <Comparative Example 1> An organic acid carrier catalyst was prepared in the same manner as in the preparation example, except that the original ZSM-5 high-silicon-aluminum-ratio molecular sieve carrier formulation was replaced by FCC carrier powder, and the rest were the same. The same manner as in Example 1 was used to catalyze the ethylene oligomerization reaction, except that the catalyst was activated and other operating conditions remained unchanged. The reaction results are shown in Table 1. The results show that this type of carrier catalyst has a high selectivity for olefin products, and there are almost no alkanes in the product composition. However, the catalyst has extremely poor reactivity to ethylene and has little reactivity. The yields of propylene and butene for 6 hours were similar to those obtained in Examples 5 and 6. <Comparative Example 2> An organic acid carrier catalyst was prepared in the same manner as in the preparation example, except that the original ZSM-5 type high-silicon-aluminum-ratio molecular sieve decorated carrier formula was replaced by FCC carrier powder, and the rest were the same. The same method as in Example 1 was used to catalyze the ethylene oligomerization reaction, except that the catalyst was activated and the reaction temperature was changed to 380 ° C, and other operating conditions were not changed. The reaction results are shown in Table 1. The results show that this type of carrier catalyst has a high selectivity for olefin products, and there are almost no alkanes in the product composition. However, the catalyst has extremely poor reactivity to ethylene and has little reactivity. The yields of propylene and butene for 6 hours were similar to those obtained in Examples 5 and 6. <Comparative Example 3> An organic acid carrier catalyst was prepared in the same manner as in the preparation example, except that the original ZSM-5 high-silicon-aluminum-ratio molecular sieve decorated carrier formula was replaced by FCC carrier powder, and the rest were the same. The same method as in Example 1 was used to catalyze the ethylene oligomerization reaction, except that the catalyst was activated and the reaction temperature was changed to 310 ° C, and other operating conditions were not changed. The reaction results are shown in Table 1. Table I The results show that this type of carrier catalyst has a high selectivity for olefin products, and there are almost no alkanes in the product composition. However, the catalyst has extremely poor reactivity to ethylene and has little reactivity. The yields of propylene and butene for 6 hours were similar to those obtained in Examples 5 and 6. Another feature of the catalyst of the present invention is that it can be implemented under conditions of medium pressure (35 kg / cm 2 ), which can reduce the reaction under low pressure conditions of 1.0 to 3.0 kg / cm 2. The catalytic procedure is safe to operate and can avoid liquid The limitation of catalyst catalytic reaction systems such as AlphaButol, a commercial technology, must be operated under medium pressure (≥35 kg / cm 2 ) or even high pressure conditions. In addition to high safety, the low-pressure solid catalyst catalytic technology provided by the present invention is separated from other procedures. The binding unit of the purification unit is relatively high. Moreover, the product of the catalytic technology of the present invention contains both propylene and butene, and the production of propylene and butene is similar. The composition of this product is different from the catalytic result of ethylene dimerization in the prior art. This can be used as ethylene dimerization or oligomerization conversion. It is another new production method for other high-value products other than butene. Therefore, the purpose of the present invention is to avoid the shortcomings derived from the current commercial technology of liquid phase reactions directly using liquid catalysts (aluminum chloride, alkylaluminum compounds, and alkyl titanates) to catalyze the production of ethylene from butene and hexene. . It not only eliminates the safety concerns of accidental combustion and explosion caused by the operation of the liquid catalyst, but also avoids the problems of waste acid, alkali, and waste ash pollution at the end of the reaction. At the same time, the organic acid metal molecular sieve carrier catalyst of the present invention is not used. Formulas containing corrosive salts such as sulfuric acid (salt), chlorine (salt), chloric acid (salt), and perchloric acid (salt), will not corrode the reactor, pipelines and equipment. It can be effectively used in low and medium pressure catalyzed ethylene oligomerization to produce higher value propylene and butene products. It can also be reused and separated to simplify the production process, thereby reducing the investment cost of operating equipment. To sum up, the present invention is a method for organic acid-decorated molecular sieve to catalyze ethylene oligomerization and produce propylene and butene at a low pressure, which can effectively improve the conventional disadvantages. The method for catalyzing the oligomerization of ethylene to produce propylene and butene is mainly to reduce the by-products of alkanes and increase the selectivity of lower olefins (propylene and butene), so as to obtain more propylene and butene products. The invention of invention can be more advanced, more practical, and more in line with the needs of users. It has indeed met the requirements for invention patent applications, and filed patent applications according to law. However, the above are only the preferred embodiments of the present invention, and the scope of implementation of the present invention cannot be limited by this; therefore, any simple equivalent changes and modifications made in accordance with the scope of the patent application and the contents of the invention specification of the present invention , All should still fall within the scope of the invention patent.