201040251 六、發明說明： 【發明所屬之技術領域】 本發明之領域係關於一種在烴流中將稀乙烯轉化為較重 的烴之裝置及方法。該等較重的烴可用作發動機燃料。 來自流體催化裂化裝置（其包含沸點低於乙烷的所有氣 體）的廢氣流通稱為乾氣體。該廢氣流經壓縮，以盡可能 移除表多C3及c：4氣體。來自廢氣流中的硫亦大多在使用胺 吸收劑之滌氣器中被吸收。殘餘的氣流稱為Fee乾氣體。 一種典型的乾氣體流包含5至50重量％乙烯、10至2〇重量％ 乙烷、5至20重量％氫、5至20重量。/。氮、〇」至5·0重量％每 種一氧化碳及二氧化碳及少於0.0 1重量。/。硫化氫及與曱烧 平衡之氨。 目月il，將β亥FCC乾氣體流送至燃燒器作為燃料氣體。每 天處理7，料9千公升（5〇,000桶）之FCC單元每天可燃燒含有 36,000 kg (40噸）乙烯作為燃料之181，〇〇〇 kg (2〇〇噸）乾氣 體。因為在燃料氣體及發動機燃料產物或純乙烯之間存在 巨大的價格差別，所以基於其經濟優勢而試圖回收此乙 烯。但是，乾氣體流包含可使寡聚合觸媒中毒之雜質且 乙細漢度過稀 濟效益。 回收乙烯沒有經 以至於藉由氣體回收系統 ，將乙稀流濃縮成液體產物之寡聚合法係一種已知㈣ :。但是’养聚合典型地涉及使用丙烯或尤其來自液化石 油氣（LPG)或脫氫原料油之丁稀，以製備汽油賴烴。乙 稀係很少用作募聚合原料油，因為其反應性極低。 147046.doc 201040251 在煉油廠物流中需利用稀乙烯。 【先前技術】 已發現’在稀乙烯流（諸如FCC乾氣體流）中的乙烯可利 用非晶體態矽石-氧化鋁觸媒上的第VIII及/或VIB族金屬催 化寡聚合形成較重的烴。該較重的烴可經分離並摻入汽油 及柴油池中。已發現，適於使乙烯寡聚合的沸石觸媒會在 雜質（諸如碳氧化物、氨及硫化氫）存在下迅速失活。該等 雜質實質上不影響在非晶體態石夕石-氧化銘载體上包含第 VIII及/或VIB族金屬之觸媒。因此，在FCC乾氣體流中之 稀乙烯可募聚合成為易於從未轉化氣體流中分離之液體燃 料產物。然後，該未轉化氣體可作為燃料氣體燃燒，但是 已移除呈較重的烴之較高價值的乙烯。 該方法及裝置可在稀物流中及在成為催化毒物之原料雜 質的存在下利用乙烯。 從本發明之描述、本文提供的附圖及請求項即可了解本 發明之附加特徵及優點。 【發明内容】 本發明可應用於任何含有乙烯及較佳為含有乙烯之稀釋 部分的烴流。合適的稀乙烯流典型地包含5至5〇重量％之 間的乙烯。FCC乾氣體流係一種合適的稀乙烯流。其他稀 乙烯流（諸如焦化乾氣體流）亦可用於本發明。由於本發明 特別適於FCC乾氣體，所以該主題應用之指述係關於利用 來自FCC乾氣體流之乙烯。 圖1中，如數字標明的組件，圖！表明通常包括Fcc單元 147046.doc 201040251 區段10及產物回收區段9〇之煉油廠集合體6。該Fcc單元 區段包括反應器12及觸媒再生器14。加工變量典型地包括 400°至600°C之裂化反應溫度及5〇〇。至9〇〇t之觸媒再生 溫度。裂化及再生均發生在506 kPa (72 5 psia)絕對壓力 下。 圖1顯不典型的FCC反應器12，纟令在分流器16中之重 質烴原料或原料油流係與從再生觸媒豎管丨8流入之再生裂 化觸媒接觸。該接觸可發生在狹窄的立管2〇中向上延伸 至反應器22的底部。原料及觸媒之接觸藉由來自流化管線 24之氣體而流化。在—項實施例中，|自觸媒的熱蒸發該 烴原料或油，然後在觸媒存在下，該烴原料裂化成為較輕 分子量的烴產物’丨中此二者皆在立管2()上端轉入反應器 22。不可避免的副反應發生在立管2〇中，且在觸媒上殘留 焦炭沉積物，降低㈣雜。然後使料包括初級分離器 26及在反應^ 22巾具有—或兩臺旋風分離器以的迴旋式分 離器，從結焦裂化觸媒中分離該裂化的輕質烴產物。氣態 的裂化產物通過產物出口 31離開反應器22至管線32，以運 送至下游產物回收區段90。肖已消耗或結焦的觸媒需要再 生供進一步使用。結焦的裂化觸媒在自氣態產物煙中分 離後，即h汽提區段34, #中氣流通過喷嘴注入，以清 洗殘留的工蒸A ο K提操作後，該結焦的觸媒通過消耗 觸媒豎管36送至觸媒再生器14。 圖1描述再^14(亦稱為燃燒室）。但是，其他種類的 再生斋亦合適。在該觸媒再生器14中，含氧氣體流（諸如 147046.doc 201040251 空氣）係通過空氣分流器38引入，與該結焦的觸媒接觸。 焦炭係從結焦的觸媒燃燒，以提供再生的觸媒及廢氣。觸 媒再生過程將大量的熱加至該觸媒中，提供能量以抵消發 生在反應器立管2〇中的吸熱裂化反應。觸媒及空氣共同沿 著位於觸媒再生器14中的燃燒器立管40向上流動且在再生 後，先藉由選別器42釋放而分離。再生的觸媒及離開選別 器42的廢氣之額外的回收係分別使用在觸媒再生器14中的 ◎ 第一及第二臺旋風分離器44、46而獲得。分離自廢氣的觸 媒通過旋風分離器44、46之氣旋料腿而進入，同時在觸媒 中相對較輕的廢氣依序離開旋風分離器44、46，且通過廢 氣管線48中的廢氣出口 47離開再生器14。再生的觸媒通過 再生觸媒豐管18而運回至立管2〇。由於焦炭燃燒的結果， 在管線48中，自觸媒再生器14頂部離開的廢氣蒸汽除包含 少量其他物質外，還包含c〇、c〇2、N2及Η2〇。熱廢氣通 過管線48中的廢氣出口 47離開再生器14，供進一步加工。 Ο 產物回收區段90係在下游與產物出口 31相連。「下游相 連」意指可操縱至少-部分流至下游相連中組份的材料來 自與其相連之組份中。「相連」意指該材料流可以在許多 戶斤列舉的組份之間操縱。在產物回收區段％中，將管線Μ 中=氣態FCC產物導入FCC主分德管柱92之較低區域。該 主管柱92係在下游與產物出口 31相連。可以分離fcc產物 的若干部分，並從包括下列組分的主管柱中取出：來自管 線93底部的重質油裝、管線料中的重質循環油流、從出口 95神獲得的管線95中的輕質循環油及從出D96a獲得的管 147046.doc 201040251 線96中的重質石腦油流。可冷卻任何或所有管線93_96， 並泵回至主管柱92，使通常在較高位置的主管柱冷卻。移 除來自主管柱92的塔頂管線97中的汽油及氣態輕質烴且在 進入主管柱接收器99之前先冷凝。該主管柱接收器"係在 下游與產物出口 31相連，該主管柱92係在上游與該主管柱 接收器99相連。「上游相連」意指可操縱至少一部分來自 上游相連的組份的材料可流至與其相連的組份。 從接收器99中的進料斗移除水性物流。此外，移除管線 ιοί中的冷凝輕質石腦油物流，同時移除管線1〇2中的塔頂 館出物流。塔頂管線102中的塔頂物流包含氣態輕質烴， 其可包括稀乙烯流。在管線101及1〇2中的物流可進入產物 回收區段90之蒸汽回收區段12〇。 該蒸汽回收區段1 20顯示為以吸收為主的系統，但是任 何蒸汽回收系統均可使用，包括低溫箱系統。爲了獲得充 分分離的輕質氣體組分，在管線丨〇2中的氣態流被壓縮進 入壓縮器104中。可使用超過一臺壓縮器，但是通常使用 雙級壓縮。在管線106中壓縮的輕質烴流藉由管線1〇7及 10 8中之物流而連接’冷卻並傳送至高壓接收器11 〇。來自 接收器110之水性物流可經過主管柱接收器99。在管線112 中包含稀乙浠流的氣態烴流則經過初級吸收器丨丨4，在其 中與來自管線101中的主管柱接收器99之不穩定的汽油接 觸’造成C#及C：2·烴之間分離。該初級吸收器1丨4在下游 與主管柱接收器99相連。在管線1 〇7中的液體c3 +物流在冷 卻前返回至管線106。來自初級吸收器114的管線116中的 147046.doc -10- 201040251 初級廢氣流包含針對本發明目的之稀乙稀。但是，爲了進 一步濃縮該乙稀流及爲了回收管線116之較重組分，可視 需要導至二級吸收器118，其中從管線95轉出的管線i2i中 • 的輕質循環油之循環物流吸收初級廢氣流中多數殘留的 C5+及某些C3_C4材料。二級吸收器118係在下游與初級吸 收，U4」目連。來自管線119中二級吸收器底部的c; +材料 含置較兩的輕質循環油通過管線95之循環泵返回至主管柱 Q 92。移除管線122的二級廢氣流中的主要包含C2_烴之乾氣 體與硫化氫、氨、碳氧化物及氫之二級吸收器ιΐ8的塔頂 館出物’以包含稀乙稀流。 將來自管線124中高壓接收器11〇之液體送至汽提塔 126。移除多數在汽提塔126塔頂餾出物中的並通過塔 頂管線108返回至管線106。來自汽提塔126的液體塔底餾 出物流通過管線128運送至脫丁烷塔管柱13〇中。來自脫丁 烷塔的管線132中之塔頂餾出物流包含C3_C4烯屬產物，同 〇 時包含安定的汽油之管線134中的底部殘留物流可供進一 步處理及運送至汽油儲存倉。 本發明之稀乙烯流可包含具有5至50重量％之間的乙烯 • 及較佳10至30重量％乙烯之FCC乾氣體流。濃度為25及55 .重里/〇之間的甲燒通常係稀乙烯流中主要組分，且乙烧之 實質含量通常為5及45重量％之間。稀乙烯流中可分別包 含1及25重量％之間及通常5至2〇重量％之氫及氮。稀乙烯 流中亦可包含飽和的水含量。若使用二級吸收器丨丨8，則 Cd含量不會超過5重量。/◦，且通常包含〇 5重量。以下之丙 147046.doc 201040251 烯。 除氫外，還有其他雜質（諸如硫化氫、4、碳氧化物及 乙炔）亦可能存在於稀乙烯流中。 已發現，在乾氣體乙烯流中的諸多雜質可能使寡聚合觸 媒中毒。氫及一氧化碳可能還原金屬位點使其失活。二氧 化碳及氨可攻擊觸媒上的酸位點。硫化氫可攻擊觸媒上的 金屬，生成金屬硫化物。乙烯可以聚合及膠合在觸媒或設 備上。 包含稀乙烯流之管線122中的二級廢氣流可引至視需要 選用的胺吸收器單元140中’以移除硫化氫而降低濃度。 濃度較稀的水性胺溶液（諸如包含單乙醇胺或二乙醇胺）通 過管線142引至吸收器140中’並與流動的二級廢氣流接 觸’以吸收硫化氫，而濃度較高的含有硫化氫之水性胺吸 收溶液通過管線143從吸收區域140移除並回收及可進一步 處理。 管線144中經胺處理的稀乙烯流可引至視需要選用的水 清洗單元146中，以移除從胺吸收器i4〇轉入的殘留的胺， 並降低管線144中稀乙稀流中的氨及二氧化竣之濃度。將 水引至管線14 5中的水清洗器中。通常輕微酸化管線丨4 5中 的水，以增強保留鹼性分子（諸如胺）。富含胺及可能含有 氨及二氧化碳中的管線147中之水性物流留在水清洗單元 146中，並可進一步處理。 然後，視需要經胺處理的稀乙烯及可能在管線148中經 水清洗的物流可在臨時保護床1 5 0中處理，以移除一或多 147046.doc -12· 201040251 種雜貝（諸如二氧化碳、硫化氫及氨），而降至較低的濃 度5亥保護床150可包含吸附劑，以吸附可能使募聚合觸 媒中骨之雜質（諸如硫化氫）。該保護床150可包含吸收一種 • 以上雜質之多種吸附劑。吸收硫化氳的典型吸收劑係201040251 VI. Description of the Invention: [Technical Field of the Invention] The field of the invention relates to an apparatus and method for converting dilute ethylene to heavier hydrocarbons in a hydrocarbon stream. These heavier hydrocarbons can be used as an engine fuel. The flow of exhaust gas from a fluid catalytic cracking unit (which contains all gases having a boiling point lower than ethane) is referred to as a dry gas. The exhaust gas is compressed to remove as much of the C3 and c:4 gases as possible. Sulfur from the exhaust stream is also mostly absorbed in a scrubber using an amine absorbent. The residual gas flow is called the Dry dry gas. A typical dry gas stream comprises from 5 to 50% by weight ethylene, from 10 to 2% by weight ethane, from 5 to 20% by weight hydrogen, from 5 to 20 weight. /. Nitrogen, bismuth" to 5.00% by weight of each of carbon monoxide and carbon dioxide and less than 0.01 weight. /. Hydrogen sulfide and ammonia balanced with helium. In the month il, the β-HCC dry gas stream is sent to the burner as a fuel gas. Processing 7 per day, 9 thousand liters (5 〇,000 barrels) of FCC unit can burn 181, 〇〇〇 kg (2 ton tons) of dry gas containing 36,000 kg (40 tons) of ethylene per day. Because of the large price difference between fuel gas and engine fuel products or pure ethylene, attempts have been made to recover this ethylene based on its economic advantages. However, the dry gas stream contains impurities which can poison the oligo-polymerization catalyst and the fineness of the fineness is exceeded. The oligo-polymerization process in which ethylene is recovered so that the ethylene stream is concentrated to a liquid product by a gas recovery system is known (4): However, 'polymerization typically involves the use of propylene or especially from liquefied petroleum oil (LPG) or dehydrogenated feedstock to produce gasoline lysine. Ethylene is rarely used as a raw material for the polymerization because it is extremely reactive. 147046.doc 201040251 Diluted ethylene is required in refinery logistics. [Prior Art] It has been found that ethylene in a dilute ethylene stream (such as a FCC dry gas stream) can be formed by catalytic oligomerization of a Group VIII and/or Group VIB metal on an amorphous meteorite-alumina catalyst. hydrocarbon. The heavier hydrocarbons can be separated and incorporated into gasoline and diesel pools. It has been found that zeolite catalysts suitable for the oligomerization of ethylene can be rapidly deactivated in the presence of impurities such as carbon oxides, ammonia and hydrogen sulfide. These impurities do not substantially affect the catalyst comprising the Group VIII and/or VIB metals on the amorphous state. Thus, the dilute ethylene in the FCC dry gas stream can be polymerized into a liquid fuel product that is easily separated from the unconverted gas stream. The unconverted gas can then be combusted as a fuel gas, but the higher value ethylene of the heavier hydrocarbons has been removed. The method and apparatus utilize ethylene in the presence of a dilute stream and in the presence of a raw material impurity that is a catalytic poison. Additional features and advantages of the invention are apparent from the description of the invention, the appended claims and claims. SUMMARY OF THE INVENTION The present invention is applicable to any hydrocarbon stream containing ethylene and preferably a dilute portion containing ethylene. A suitable dilute ethylene stream typically comprises between 5 and 5 weight percent ethylene. The FCC dry gas stream is a suitable stream of dilute ethylene. Other dilute ethylene streams, such as coked dry gas streams, can also be used in the present invention. Since the invention is particularly suitable for FCC dry gases, the subject application is directed to utilizing ethylene from the FCC dry gas stream. In Figure 1, the components as indicated by the numbers, Figure! It is indicated that the refinery assembly 6 of the Fcc unit 147046.doc 201040251 section 10 and the product recovery section 9〇 is generally included. The Fcc unit section includes a reactor 12 and a catalyst regenerator 14. Processing variables typically include a cracking reaction temperature of 400 to 600 ° C and 5 Torr. Catalyst regeneration temperature up to 9〇〇t. Both cracking and regeneration occur at 506 kPa (72 5 psia) absolute pressure. Figure 1 shows an exemplary FCC reactor 12 in which the heavy hydrocarbon feedstock or feedstock stream in the splitter 16 is contacted with a regenerated cracking catalyst flowing from the recycle catalyst riser 8 . This contact can occur in the narrow riser 2〇 extending up to the bottom of the reactor 22. The contact of the feedstock and the catalyst is fluidized by the gas from the fluidization line 24. In the embodiment, the hydrocarbon feedstock or oil is thermally evaporated from the catalyst, and then the hydrocarbon feedstock is cracked into a lighter molecular weight hydrocarbon product in the presence of a catalyst, both of which are in riser 2 ( The upper end is transferred to the reactor 22. The inevitable side reaction occurs in the riser 2, and coke deposits remain on the catalyst, reducing (four) impurities. The cracking light hydrocarbon product is then separated from the coked cracking catalyst by including a primary separator 26 and a swirling separator having two or two cyclones in the reaction vessel. The gaseous cracked product exits reactor 22 to line 32 through product outlet 31 for transport to downstream product recovery section 90. The catalyst that Xiao has consumed or coked needs to be regenerated for further use. After the coking cracking catalyst is separated from the gaseous product smoke, that is, the h stripping section 34, #中流流 is injected through the nozzle to clean the residual steaming A ο K operation, the coking catalyst passes through the consumption touch The media riser 36 is sent to the catalyst regenerator 14. Figure 1 depicts a further 14 (also known as a combustion chamber). However, other types of rejuvenation are also suitable. In the catalyst regenerator 14, an oxygen-containing gas stream (such as 147046.doc 201040251 air) is introduced through the air splitter 38 in contact with the coked catalyst. The coke is burned from the coked catalyst to provide regenerated catalyst and exhaust. The catalyst regeneration process adds a significant amount of heat to the catalyst to provide energy to counteract the endothermic cracking reaction that occurs in the reactor riser. The catalyst and air together flow upwardly along the burner riser 40 located in the catalyst regenerator 14 and, after regeneration, are first separated by the selector 42 release. The additional recovery of the regenerated catalyst and the exhaust gas leaving the separator 42 is obtained using the first and second cyclones 44, 46 in the catalyst regenerator 14, respectively. The catalyst separated from the exhaust gas enters through the cyclone legs of the cyclones 44, 46 while the relatively light exhaust gases in the catalyst sequentially exit the cyclones 44, 46 and pass through the exhaust gas outlets 47 in the exhaust gas line 48. Leave the regenerator 14. The regenerated catalyst is transported back to the riser 2 via the regenerated catalyst manifold 18. As a result of coke combustion, in line 48, the exhaust gas leaving the top of the catalyst regenerator 14 contains c〇, c〇2, N2, and Η2〇 in addition to a small amount of other materials. Hot exhaust gases exit the regenerator 14 through an exhaust gas outlet 47 in line 48 for further processing. The product recovery section 90 is connected downstream to the product outlet 31. "Downstream connection" means the manipulation of at least a portion of the material flowing to the downstream connected component from the component to which it is attached. "Connected" means that the stream of material can be manipulated between a number of components listed. In the product recovery section %, the pipeline Μ medium = gaseous FCC product is introduced into the lower region of the FCC main branch column 92. The main column 92 is connected downstream to the product outlet 31. Several portions of the fcc product can be separated and taken from the main column comprising the following components: heavy oil from the bottom of line 93, heavy cycle oil in the feed, line 95 from outlet 95 Light cycle oil and heavy naphtha stream from line 147046.doc 201040251 line 96 obtained from D96a. Any or all of the lines 93_96 may be cooled and pumped back to the main column 92 to cool the main column, which is typically at a higher position. The gasoline and gaseous light hydrocarbons in the overhead line 97 from the main column 92 are removed and condensed prior to entering the main column receiver 99. The main column receiver &# is connected downstream to the product outlet 31, which is connected upstream to the main column receiver 99. "Upstream connection" means that at least a portion of the material from the upstream connected components can be manipulated to flow to the components associated therewith. The aqueous stream is removed from the feed hopper in the receiver 99. In addition, the condensed light naphtha stream in line ιοί is removed while the overhead stream in line 1〇2 is removed. The overhead stream in overhead line 102 comprises gaseous light hydrocarbons, which may include a dilute ethylene stream. The streams in lines 101 and 1 can enter the vapor recovery section 12 of product recovery section 90. The vapor recovery section 110 is shown as an absorption based system, but any vapor recovery system can be used, including a cryostat system. In order to obtain a sufficiently separated light gas component, the gaseous stream in line 丨〇2 is compressed into compressor 104. More than one compressor can be used, but two-stage compression is usually used. The light hydrocarbon stream compressed in line 106 is connected by the stream in lines 1〇7 and 108 to be cooled and transferred to high pressure receiver 11〇. The aqueous stream from receiver 110 can pass through main column receiver 99. The gaseous hydrocarbon stream containing the dilute ethylene stream in line 112 passes through the primary absorber 丨丨4 where it contacts the unstable gasoline from the main column receiver 99 in line 101 'causing C# and C:2. hydrocarbons Separated between. The primary absorber 1丨4 is connected downstream to the main column receiver 99. The liquid c3+ stream in line 1 〇7 is returned to line 106 before cooling. The 147046.doc -10- 201040251 primary exhaust stream from line 116 from the primary absorber 114 contains the dilute ethylene for the purposes of the present invention. However, in order to further concentrate the ethylene stream and to recover the heavier components of line 116, it may be directed to secondary absorber 118, wherein the recycle stream of light cycle oil from line i2i from line 95 is absorbed by the primary stream. Most of the residual C5+ and some C3_C4 materials in the exhaust stream. The secondary absorber 118 is downstream and primaryly adsorbed, U4". From the bottom of the secondary absorber in line 119 c; + material containing two of the light cycle oil is returned to the main column Q 92 via a circulation pump of line 95. The overhead gas stream containing the C2_hydrocarbons in the secondary exhaust stream of line 122 is removed from the overheads of the secondary absorbers of hydrogen sulfide, ammonia, carbon oxides and hydrogen to contain a dilute ethylene stream. The liquid from the high pressure receiver 11 in line 124 is sent to stripper 126. Most of the overhead in stripper 126 is removed and returned to line 106 via overhead line 108. The liquid bottoms stream from stripper 126 is passed via line 128 to the debutanizer column 13 crucible. The overhead stream from line 132 of the debutanizer column contains the C3_C4 olefinic product, while the bottom residue stream in line 134 containing the stabilized gasoline is available for further processing and delivery to the gasoline storage bin. The dilute ethylene stream of the present invention may comprise a FCC dry gas stream having between 5 and 50% by weight of ethylene and preferably from 10 to 30% by weight of ethylene. Concentrations of 25 and 55. The calcination between the aliquots/〇 is usually the main component in the dilute ethylene stream, and the actual content of the ethidium is usually between 5 and 45% by weight. The dilute ethylene stream may comprise between 1 and 25% by weight and usually between 5 and 2% by weight of hydrogen and nitrogen, respectively. The saturated ethylene content can also be included in the dilute ethylene stream. If a secondary absorber 丨丨8 is used, the Cd content will not exceed 5 weights. /◦, and usually contains 〇 5 weight. The following C 147046.doc 201040251 olefin. In addition to hydrogen, other impurities such as hydrogen sulfide, carbon monoxide, and acetylene may also be present in the dilute ethylene stream. It has been found that many impurities in the dry gas ethylene stream can poison the oligomeric catalyst. Hydrogen and carbon monoxide may reduce the metal sites to inactivate them. Carbon dioxide and ammonia attack the acid sites on the catalyst. Hydrogen sulfide can attack metals on the catalyst to form metal sulfides. Ethylene can be polymerized and glued onto the catalyst or equipment. The secondary exhaust stream in line 122 containing the dilute ethylene stream can be directed to the desired amine absorber unit 140 to reduce the concentration of hydrogen sulfide. The dilute aqueous amine solution (such as comprising monoethanolamine or diethanolamine) is passed through line 142 to absorber 140 and is in contact with the flowing secondary exhaust stream to absorb hydrogen sulfide, while the higher concentration contains hydrogen sulfide. The aqueous amine absorption solution is removed from the absorption zone 140 via line 143 and recovered and may be further processed. The amine treated dilute ethylene stream in line 144 can be directed to an optional water scrubbing unit 146 to remove residual amines from the amine absorber i4 and reduce the lean ethylene stream in line 144. The concentration of ammonia and cerium oxide. The water is directed to a water scrubber in line 14 5 . The water in the line 丨4 5 is typically slightly acidified to enhance retention of basic molecules such as amines. The aqueous stream in line 147 rich in amines and possibly in ammonia and carbon dioxide is retained in water wash unit 146 and may be further processed. The amine treated dilute ethylene and possibly water-washed stream in line 148 may then be treated in a temporary guard bed 150 to remove one or more 147046.doc -12. 201040251 species (such as Carbon dioxide, hydrogen sulfide, and ammonia), while falling to a lower concentration, the 5th guard bed 150 may contain an adsorbent to adsorb impurities (such as hydrogen sulfide) that may cause bone in the polymerization catalyst. The guard bed 150 can comprise a plurality of adsorbents that absorb one or more of the above impurities. Typical absorbent system for absorbing barium sulfide
ADS-12、吸收c〇的係ADS-106及吸收氨的係u〇P MOLSIV 3A(白t•購自uop，lLC)。該等吸附劑可混入單獨床中或可 排列在連續的床中。 ◎ 管線151中可能經胺處理、可能經水清洗及可能經過吸 附處理以移除更多的硫化氫、氨及一氧化碳之稀乙烯流通 常具有至少一種下列雜質濃度：〇.i重量％至至多5.〇重量％ 一氧化碳及/或〇· 1重量％至至多5.0重量％二氧化碳、及/或 至少1 wppm至至多500 wppm硫化氫及/或至少1至至多5〇〇 wppm氨、及/或至少5至至多20重量％氫。該等種類雜質之 存在及其濃度可隨稀乙烯流之處理及來源而改變。 管線151將稀乙烯流運送至壓縮器152，以加壓至反應器 ◎ 壓力。該壓縮器152在下游與主管柱92、產物回收段9〇及 產物出口 3 1相連。該經壓縮的稀乙烯流可壓縮至至少 3,550 kPa (500 psia)且或許不超過 10,445 kPa (1500 psia)及 宜在 4,930 kPa (700 psia)與 7,687 kPa (1100 pSia)之間。該 稀乙烯流最好加壓至高於乙浠之臨界壓力（其係純乙浠之 4,992 kPa (724 psia))，以避免加快觸媒失活。壓縮器152 可包含一或多個具有級間冷卻之裝置。可能需要加熱器以 使該經壓縮的物流升至反應溫度。將管線154中的經壓縮 的稀乙烯運送至寡聚合反應器156。 147046.doc -13· 201040251 寡聚合反應器156係在下游分別與壓縮器i52及初級及二 級吸收urn及m相連。該寡聚合反應器較佳包含固定催 化劑床15 8。#乙烯原料流較佳在向下流動操作中與觸媒 接觸。但是’上升流操作可能適宜。觸媒較佳係具有來自 使用Chemical Abstracts Service之週期表標記法中的第νιπ 及/或VIB族之金屬的非晶體態矽石_氧化鋁基質。在一態 樣中，該觸媒使用第VIII金屬，並輔以第VIB族金屬。: 一態樣中，該觸媒之矽石對氧化鋁比為至多3〇及較佳至多 20。典型地，由於石夕石及氧化銘僅在基質中，所以對於該 觸媒及及基貝’石夕石對氧化銘比相同。該金屬可浸潰於石夕 石-氧化鋁基質上或與其進行離子交換。亦考慮共研磨。 本發明之觸媒之低溫酸度比可為至少〇15，宜為〇 2及較佳 大於0.25 ’其係藉由如下文描述的氨溫程控脫附法(氨 TPD)測疋。此外，合適觸媒可具有藉由氮ΒΕτ測定的及 400 m2/g之間的表面積。 本發明之較佳的募聚合觸媒係如下描述。該較佳的寡聚 合觸媒包含非晶體態矽石_氧化鋁載體。本發明中使用的 觸媒載體之一組分係氧化鋁。該氧化鋁可係不同的水合氧 化鋁或氧化鋁凝膠（諸如勃畝石或擬勃畝石結構之α•氧化 鋁一水化物、水鉛氧石結構之α_氧化鋁三水化物、拜耳石 結構之β-氧化鋁三水化物及類似物）。特別佳的氧化鋁係購 自 Sasol North America Alumina Product Group之商標名稱 為Catapal。该材料係極高純度之α氧化鋁一水化物（擬勃 畝石），已顯示其在高溫煅燒後生成高純度γ_氧化鋁。該觸 147046.doc •14- 201040251 、载體之另、组分係非晶體態矽石-氧化鋁。矽石對氧化 匕為2.6之合適矽石-氧化鋁購自日本JGC之子公司 CCIC。 • 本發明中製備觸媒所使用的另-組分係界面活性劑。該 纟&劑係較佳與上文描述的氧化及⑦石·氧化链粉 末混合。所得界面活性劑、氧化鋁及矽石-氧化鋁之混合 物隨後依下文描述進行成型、乾燥及锻燒。該锻燒法可藉 〇 *燃燒，有效移除界面活性劑之有機組分，但是僅在該界 面活性劑依照本發明忠實執行其功能之後進行。依照本發 月可矛J用任何合適的界面活性劑。較佳的界面活性劑係選 自一系列售自Solvay S.A·商標為「Antar〇x」之界面活性 劑。该「Antarox」界面活性劑之一般特徵係經改質的直 鏈月曰肪族聚酸’ 係、低^泡性生物降解的清潔劑及潤濕 劑。 合適的矽石-氧化鋁混合物係按體積比例混合矽石-氧化 〇 結及氧化銘而製備，以獲得所需的石夕石對氧化鋁比。在一 項實施例中，85重量％石夕石對氧化銘比為26之非晶體態石夕 石-氧化鋁及15重量％氧化鋁粉末可提供合適的載體。在一 $實施例中，不是85-比_15比例之非晶體態石夕石.氧化㈣ 氧化鋁比例可能合適，只要載體之最終矽石對氧化鋁比係 適宜至多30及較佳至多20即可。 可使用任何合適的方法將界面活性劑併入矽石_氧化鋁 及氧化紹混合物中。該界面活性劑較佳係在該混合及形成 氧化銘及石夕石-氧化紹期間混入。較佳的方法係在形成最 147046.doc -15- 201040251 終載體4，將界面活性劑之水性溶液混入氧化鋁及矽石_ 氧化鋁之摻合物中。較佳地，該界面活性劑係呈糊狀物或 團狀物，其基於氧化銘及石夕石-氧化铭之重量計之含量為 〇.〇1至10重量％。 可將單質子酸（諸如硝酸或甲酸）加至在水性溶液中之混 合物中，以膠溶結合劑中之氧化銘。可將額外的水加至該 混合物中，以提供足夠的濕度，構成足夠稠度之團狀物， 供進行擠壓或噴霧乾燥。 該糊狀物或團狀物可製備成微粒狀的形式，其中較佳的 °係將氧化、碎石_氧化銘、界面活性劑及水之團狀 此σ物自具有所需的大小及形狀的開口之模具中擠出，然 後將該擠出之物體分成所需長度的擠出物並乾燥。可利用 另一個般燒步驟對擠出物提供附加強度。通常，锻燒係在 溫度鳩如啊⑻饥⑴⑽㈠之乾空氣中進行。 擠出的微粒可具有任何合適的截面形狀，亦即對稱或不 對稱’但是多數常具有對稱的截面形狀，較佳為球形、圓 柱形或多葉形。該微粒之截面直徑可小至40 μ1η;但是， 其通常為0.635 mm(0·25英寸）至u 7 mm(〇 5英寸），較佳為 〇.79mm(1/32英寸）至6.35咖（0.25英寸），及最佳為0.06 mm(l/24央寸）至4·23 _⑽英寸）。較佳的觸媒組態係類 似（例如）US 4,028 227 少 ϋΐδΒΟΑίβ _ ，之圖8及8Α中顯示的三葉草截面形 狀。較佳的三葉草形狀之微粒係截面的每個「葉子」係界 定在直徑在〇.51mm(0.02英寸）至127_(〇5英寸）之間的 270。圓弧而定義。其他較佳的微粒係彼等具有四葉形截面 147046.doc -16 - 201040251 形狀（G 3不對稱形狀及對稱形狀（諸如US 4,028,227之圖 1〇中）)者。 本文使用的非晶體態矽石_氧化鋁載體之典型特徵係總 Μ孔隙體積、平均孔隙直徑及表面積應足夠大至提供大量 Μ間及面積使活性金屬組分沉積。藉由常規的汞孔隙率 方法測定的載體之總體孔隙體積通常係〇2至2G ee/克，較 佳0·25至1.0 cc/克及最佳〇3至〇9 克。通常，孔隙直徑 ❹ 大於100埃之载體的空隙體積數係小於〇.! ec/克，較佳小 於0.08 cc/克及最佳小於〇 〇5 cc/克。藉由b ε τ方法測定的 表面積典型地係高於50 ni2/克，例如，高於2〇〇 m2/克，較 佳至少250 m2/克，及最佳300 m2/克至4〇〇 ^/克。 製備觸媒時，該載體材料藉由單一浸潰或多重浸潰已烺 燒的非晶體態耐熔氧化物載體微粒（具有一或多個至少一 種來自週期表第νιπ或VIB族之金屬組分的前體）而化合。 第VIII族金屬（較佳為鎳）之含量濃度應為05至15重量％， Q 而第VIB族金屬（較佳為鎢）之含量濃度應為〇至12重量％。 該浸潰法藉由此項技術中已知之任何方法完成，例如，喷 灑浸潰法，其中將含有溶解形式的金屬前體的溶液噴灑在 •載體微粒上。另一方法係多次浸潰方法，其中該載體材料 與經或不經間歇乾燥的浸潰溶液進行重複接觸。另一種方 法包括將載體浸入大量浸潰溶液中或將載體在其中循環， 及又一方法係孔隙體積或孔隙飽和技術，其中將載體微粒 引至容量僅夠填充載體孔隙之浸潰溶液中。有時可修改孔 隙飽和技術，以利用比僅夠填充孔隙之容量少10%至多 147046.doc •1*7- 201040251 ι〇°/。之間之浸潰溶液。 若該活性金屬前體係藉由浸潰法併入，隨後的或第二種 煅燒法將在高溫下（例如，399。及760°C之間（75〇。及 1400°F)) ’將金屬轉變為其等各自的氡化物形式。 呆些 情況中’可繼各活性金屬分別浸潰之後進行煅燒。接續: 煅燒法可產生含有呈其各氧化物形式之活性金屬的觸媒。 本發明較佳的募聚合觸媒具有浸潰〇.5至15重量％錄的非 晶體態矽石-氧化鋁基質，其呈3·175 mm (〇125英寸）擠出 物形式且密度為〇.45至0.65 g/ml。亦包括藉由其他方法（諸 如離子交換及共研磨）併入載體上之金屬。 啊秌刊用稽田热知的油滴法（其允f 使用大球形式的載體)製成的共膠凝化矽石-氧化鋁载體: 例如’用於作為氧化銘來源之氧化溶膠係與作為石夕石 源的酸化水玻璃溶液合併，且該混合物係進一步 =劑（例如’尿素、六亞曱基四胺或其混合物）合併。免 旋轉圓盤，將仍低於膠凝溫度之混合物排 在膠凝溫度之孰，、&、义祕 中，在通過、… 該混合物呈滴液分散… 在通過通相間形成球形凝膠 佳係藉由以下方法匍供孙 /乳化鋁岭膠乾 或去離子之W 氧化紹顆粒與—^量已處理 及形成 7 °併’添加足量鹽酸，以消化-部分鋁金屬 及形成需要的溶膠 / 丨刀姑金屬 度所致。 〇 心速率係為混合物之回流溫 147046.doc 201040251 並衰終用水清洗。油浴中混合物的適當的膠凝化及隨後凝 膠球的熟化在低於48.9°C(120°F)不容易完成，及在 98.9C(210F)下，氣體的快速散發容易使球體破裂及減 弱。在成型及熟化步驟期間，藉由維持足夠的超大氣壓力 以維持液相中的水，使用較高的溫度經常可改進結果。若 •該凝膠微粒係在超大氣壓力下熟化，則不需要鹼性熟化步 驟。 ◎ 該球體係用水清洗，較佳利用含有少量氫氧化銨及/或 叙之水。清洗後，在溫度93.3°C (200°F)至3 15°C (600°F ) 下乾燥6至24小時或更久，且然後在溫度426.67 °C (800 至760°C(140(TF)下煅燒2至12小時或更久。 苐VIII族組勿及第VIB族組分係由藉由任何合適的共浸 潰技術之共膠凝化矽石-氧化鋁載體材料組成。因此，該 載體材料可浸沒、浸潰或懸浮，或浸入含有可溶性第νιπ 族鹽及可溶性第VIB族鹽之水性浸潰溶液中。一種合適的 〇 方法包括將載體材料浸入浸潰溶液中，及在旋轉式蒸汽乾 燥器中蒸發至乾燥，該浸潰溶液之濃度應確保最終觸媒複 &物所包3之錄對錄加上嫣的原子比為〇.1至〇.3。另一種 •合適的方法包括在室溫下，將載體材料浸入水性浸潰溶液 中，直至溶液完全滲透載體為止。在吸收浸潰溶液後，該 載體瀝乾游離之表面液體，並在移動帶煅燒爐中乾燥。 該觸媒複合物通常在煅燒之前先在溫度9 3 · 31 (2 〇 〇卞）至 260 C (500 F )下乾燥1至1 〇小時。根據本發明，锻燒係在氧 化氣體中，溫度371。(：（700卞）至650\：(1200Τ)下進行。雖 147046.doc •19- 201040251 然可使用其他包含分子態氧之氣體，但是該氧化氣體以空 氣為合適。 另一合適的觸媒係浸潰〇.5至15重量。/。鎳及〇至12重量％ 鎢之經油滴處理的矽石_氧化鋁球形載體，其直徑為3175 mm(0.125英寸）。可考慮其他合適的金屬併入方法。對於 其他觸媒之適宜密度範圍可在0.60及0.70 g/mL之間。 该稀乙烯進料可在溫度2〇〇t3&4〇(rc之間與募聚合觸媒 接觸。該反應主要發生在GHSV 50至1000 hr-1以乙烯為基 礎之氣相中。已驚奇地發現，儘管原料中存在使觸媒中毒 及使乙烯變稀之雜質，但是在原料氣流中仍至少4〇重量％ 及夕達75重量/。之乙烯轉化為較重的烴。該乙烯首先在觸 媒上募聚合為較重的烯烴。某些較重的烯烴可在觸媒上環 化’及在氫的存在下，將促進該等烯烴轉化為鏈烧煙，其 係均比乙稀重的烴。 儘管原料不純，該觸媒仍可保持安定，但是其可在失活 時再生。合適的再生條件包括（例如）使觸媒在原位，於 5〇〇。(：熱空氣中處理3小時。經再生的觸媒之活性及選擇性 係與新鮮的觸媒相當。 來自管線160中的寬令人； — "0反應器之券聚合產物流可運送 至养聚合分離器162中，JL可為銪留认面外 液體流中分離。兮寡…:為間早的圓同以將氣態流從 應器: I 162係在下游與寡聚合反 1 塔頂官線丨64中包含輕質氣體（諸如氬 ^ 元、乙烷、未反應的烯烴及輕質雜質)之氣離產物 流可運送至燃燒單元166，以）孔〜、產物 乂在g線167中生成物流。或 147046.doc -20· 201040251 者在&頂管線164中的氣態產物可燃燒，以點燃加熱器 (無顯不）及/或提供燃料氣來源轉入燃氣渦輪機（無顯示）以 =電★塔頂官線164在上游與燃燒單元166相連。來自募聚 刀離器162笞線168中的包含較重質烴之液體底部殘留物 °下降至閥門上’並再循環回至產物分離區段9〇。再循 •環管線168係在下游與募聚合分離器162之底部殘留物169 相連因此，主官柱92係在下游及上游與寡聚合反應器 相連底部殘留物氣流較佳地通過再循環管線！ 68再循 %至位於重質石腦油出口 96a及輕質循環油出口 95a之間的 主管柱92。或者，由再循環管線168送進輕質循環油管線 95或重質石腦油管線96。該再循環管線在下游與寡聚合反 應器156=連及在上游與主管柱92相連。或者，在管線16〇 或168之寡聚合產物可經或不經飽和並運送至無須再循環 至產物分離區域9〇之燃料箱中β 【實施方式】 〇 本發明之用途可藉由以下實例證明。 實例1 利用本文上述針對本發明其他觸媒之製程，合成承載在 非晶體態矽石-氧化鋁經油滴的球形基質上之鎳及鎢。該 金屬包含占該觸媒之1.5重量％鎳及η重量％鎢。該等球形 基質具有直徑3.1 75 mm。該觸媒之矽石對氧化鋁之比為 3 ’ 禮度 0.641 g/mL 及表面積 371 m2/g。 實例2 擠出的非晶體態矽石-氧化鋁之合成法係將非晶體態矽 I47046.doc -21 - 201040251 石-氧化銘（其藉由CCIC提供的矽石對氧化鋁比為2.6)及以 商標名Catapal提供之擬勃故石，依重量比為85-至-15組 合。s亥擬勃故石先利用；g肖酸膠溶後’再與非晶體態石夕石_ 氧化紹混合。提供商標名Antarox之界面活性劑及足夠潤 濕團狀物的水添加至該混合物中。該觸媒團狀物自圓柱形 模板中的1.59 mm開口擠出並在分成片段後，於550°C下煅 燒。最終的觸媒由85重量％矽石-氧化鋁及丨5重量％氧化鋁 組成’其矽石對氧化鋁比為1.92及表面積為268 m2/g。 實例3 將3.37克Ni(N〇3V6H2〇溶於32.〇8克去離子水中。鎳溶 液分成四份添加並在添加之間劇烈震盪，使該鎳溶液與實 例2之擠出的非晶體態矽石_氧化鋁接觸。生成淺綠色的擠 出物。然後，該擠出物在1HTC下乾燥3小時，然後以2<t/min 升溫至500°C進行椴燒並先在50{rc維持3小時後再冷卻至 室溫，使該鎳金屬而轉化為氧化物形式。發現淺灰色擠出 物包含1·5重量％鎳。 實例4 矽石對氧化鋁之比為40的ΜΤΤ沸石樣品係購自Ze〇lyst C〇rP〇rati〇I^該MTT沸石與擬勃畝石組合並先通過圓柱形 模板中的3.175開口中擠出後，再煅燒至55〇〇c。所完成的 觸媒由80重量％ MTT沸石及2〇重量％氧化鋁組成。 實例5 —在 280。(：、6,895 kPa 〇〇〇〇 psig)、训 〇ghsv(烯烴氣體 每小時間隔速率）、在10 mL觸媒上的固定床操作中測= 147046.doc 201040251 實例1觸媒對烯烴寡聚合之作用。該進料由3〇重量％ C2H4 及7〇重里％ CH4組成。結果如表i所示。 實例6ADS-12, ADS-106 which absorbs c〇, and U〇P MOLSIV 3A which absorbs ammonia (white t• purchased from uop, lLC). The adsorbents can be mixed into separate beds or can be arranged in a continuous bed. ◎ The dilute ethylene stream in line 151, which may be treated with an amine, possibly with water, and possibly subjected to an adsorption treatment to remove more hydrogen sulfide, ammonia and carbon monoxide, typically has at least one of the following impurity concentrations: 〇.i% by weight up to 5 % by weight of carbon monoxide and / or 〇 · 1% by weight up to 5.0% by weight of carbon dioxide, and / or at least 1 wppm up to 500 wppm of hydrogen sulfide and / or at least 1 up to 5 〇〇 wppm of ammonia, and / or at least 5 Up to 20% by weight of hydrogen. The presence of such impurities and their concentrations may vary with the treatment and source of the dilute ethylene stream. Line 151 carries the dilute ethylene stream to compressor 152 for pressurization to reactor ◎ pressure. The compressor 152 is downstream connected to the main column 92, the product recovery section 9A, and the product outlet 31. The compressed dilute ethylene stream can be compressed to at least 3,550 kPa (500 psia) and perhaps no more than 10,445 kPa (1500 psia) and preferably between 4,930 kPa (700 psia) and 7,687 kPa (1100 pSia). The dilute ethylene stream is preferably pressurized to a critical pressure above acetamidine (which is 4,992 kPa (724 psia) of pure ethyl hydrazine) to avoid accelerated catalyst deactivation. Compressor 152 can include one or more devices with interstage cooling. A heater may be required to raise the compressed stream to the reaction temperature. The compressed dilute ethylene in line 154 is passed to an oligomerization reactor 156. 147046.doc -13· 201040251 The oligomerization reactor 156 is connected downstream to the compressor i52 and the primary and secondary absorption urn and m, respectively. The oligomerization reactor preferably comprises a fixed catalyst bed 15 8 . The #ethylene feed stream is preferably contacted with the catalyst during the downward flow operation. However, an upflow operation may be appropriate. Preferably, the catalyst has an amorphous state vermiculite-alumina matrix from a metal of the group νιπ and/or VIB in the periodic table labeling of Chemical Abstracts Service. In one aspect, the catalyst uses a metal of the VIII and is supplemented with a Group VIB metal. In one aspect, the catalyst has a vermiculite to alumina ratio of at most 3 Å and preferably at most 20. Typically, since Shi Xi Shi and Oxidation are only in the matrix, the catalyst and the Kibe stone are the same as the oxidation. The metal can be impregnated onto or ion exchanged with the Shishishi-alumina substrate. Co-milling is also considered. The catalyst of the present invention may have a low acidity ratio of at least 〇15, preferably 〇 2 and preferably more than 0.25 Å, which is measured by an ammonia temperature programmed desorption method (ammonia TPD) as described below. Further, a suitable catalyst may have a surface area measured by nitrogen ΒΕτ and between 400 m2/g. Preferred polymeric catalysts of the present invention are described below. The preferred oligomeric catalyst comprises an amorphous vermiculite-alumina support. One of the components of the catalyst carrier used in the present invention is alumina. The alumina may be a different hydrated alumina or alumina gel (such as a-alumina monohydrate of boehmite or pseudo-acre structure, alpha-alumina trihydrate of water lead-oxygen structure, Bayer stone) Structure of β-alumina trihydrate and the like). A particularly good alumina system is available from Sasol North America Alumina Product Group under the trade name Catapal. This material is a very high purity alpha alumina monohydrate (pseudo-boehmite) which has been shown to produce high purity gamma-alumina after calcination at elevated temperatures. The touch 147046.doc •14- 201040251, the other component of the carrier is amorphous amorphous vermiculite-alumina. A suitable vermiculite-alumina with a strontium oxide of 2.6 is purchased from CCIC, a subsidiary of Japan JGC. • A further component surfactant used in the preparation of the catalyst in the present invention. The oxime & agent is preferably admixed with the oxidized and 7 stone oxidized chain powders described above. The resulting mixture of surfactant, alumina and vermiculite-alumina was subsequently shaped, dried and calcined as described below. The calcination method can effectively remove the organic component of the surfactant by combustion, but only after the surfactant faithfully performs its function in accordance with the present invention. Any suitable surfactant can be used in accordance with this month. Preferred surfactants are selected from a series of surfactants sold under the trademark "Antar〇x" by Solvay S.A. The "Antarox" surfactant is generally characterized by a modified linear lunar adipose polyacid system, a low-foaming biodegradable detergent and a wetting agent. A suitable vermiculite-alumina mixture is prepared by mixing vermiculite-oxidized yttrium and oxidized in a volume ratio to obtain the desired ratio of shishi to alumina. In one embodiment, 85% by weight of Shishishi provides a suitable support for the amorphous state of the cerium-alumina-alumina and 15% by weight of alumina powder. In an embodiment, an amorphous state is not a ratio of 85 to -15. The proportion of oxidized (tetra) alumina may be suitable as long as the final vermiculite to alumina ratio of the carrier is at most 30 and preferably at most 20 can. The surfactant can be incorporated into the vermiculite-alumina and the oxidized mixture using any suitable method. Preferably, the surfactant is incorporated during the mixing and formation of Oxidation and Shishishi-Oxidation. The preferred method is to form the final carrier 4 of 147046.doc -15-201040251, and the aqueous solution of the surfactant is mixed into the blend of alumina and vermiculite-alumina. Preferably, the surfactant is in the form of a paste or agglomerate based on the weight of Oxidation and Shi Xishi-Oxidation: from 1 to 10% by weight. A monoprotic acid such as nitric acid or formic acid may be added to the mixture in the aqueous solution to oxidize the oxidizing agent in the binder. Additional water can be added to the mixture to provide sufficient moisture to form a dough of sufficient consistency for extrusion or spray drying. The paste or dough can be prepared in a particulate form, wherein the preferred phase is oxidized, crushed, oxidized, surfactant, and water sigma have the desired size and shape. The open mold is extruded and the extruded object is then divided into extrudates of the desired length and dried. Additional firing steps can be used to provide additional strength to the extrudate. Usually, calcination is carried out in dry air at a temperature of, for example, (8) hunger (1) (10) (a). The extruded particles may have any suitable cross-sectional shape, i.e., symmetrical or asymmetrical, but most often have a symmetrical cross-sectional shape, preferably spherical, cylindrical or multilobal. The cross-sectional diameter of the microparticles can be as small as 40 μl η; however, it is usually 0.635 mm (0·25 inches) to u 7 mm (〇 5 inches), preferably 〇.79 mm (1/32 inches) to 6.35 coffees ( 0.25 inches), and preferably 0.06 mm (l/24 CC) to 4.23 _ (10) inches). The preferred catalyst configuration is similar to, for example, US 4,028 227, less ϋΐδΒΟΑίβ _ , and the cross-sectional shape of the clover shown in Figures 8 and 8Α. Each "leaf" of the preferred clover-shaped particle section is defined by 270 having a diameter between 51.51 mm (0.02 inch) and 127_(〇5 inch). Defined by an arc. Other preferred microparticles have a four-lobed cross-section 147046.doc -16 - 201040251 shape (G 3 asymmetric shape and symmetrical shape (such as in Figure 4 of US 4,028,227)). The typical characteristics of the amorphous meteorite-alumina support used herein are that the total pore volume, average pore diameter and surface area should be sufficiently large to provide a large amount of inter-turn and area for the deposition of the active metal component. The overall pore volume of the support as determined by conventional mercury porosimetry is typically from 2 to 2 G ee per gram, preferably from 0. 25 to 1.0 cc per gram and optimal from 〇 3 to 〇 9 grams. Generally, the number of voids of the support having a pore diameter 大于 greater than 100 angstroms is less than 〇.! ec/g, preferably less than 0.08 cc/g and most preferably less than 〇 5 cc/g. The surface area as determined by the b ε τ method is typically above 50 ni 2 /g, for example, above 2 〇〇 m 2 / gram, preferably at least 250 m 2 / gram, and optimally 300 m 2 / gram to 4 〇〇 ^ /g. When the catalyst is prepared, the carrier material is immersed in a single-impregnated or multi-impregnated ignited amorphous refractory oxide carrier particle (having one or more at least one metal component from the νιπ or VIB group of the periodic table) The precursors are combined. The Group VIII metal (preferably nickel) should be present in an amount of from 05 to 15% by weight, Q, and the Group VIB metal (preferably tungsten) should be present in an amount of from 〇 to 12% by weight. The impregnation method is accomplished by any method known in the art, for example, a spray impregnation method in which a solution containing a metal precursor in dissolved form is sprayed onto the carrier particles. Another method is a multiple impregnation process in which the support material is repeatedly contacted with an impregnation solution with or without intermittent drying. Another method involves immersing the support in a large amount of impregnation solution or circulating the support therein, and yet another method is a pore volume or pore saturation technique in which the carrier particles are introduced into an impregnation solution having a capacity sufficient to fill the pores of the support. It is sometimes possible to modify the pore saturation technique to take up 10% less than the capacity to fill only the pores. 147046.doc •1*7- 201040251 ι〇°/. The solution between the impregnations. If the active metal pre-system is incorporated by impregnation, the subsequent or second calcination process will be at elevated temperatures (eg, between 399 and 760 ° C (75 〇 and 1400 ° F)) Change to its own form of telluride. In some cases, the calcination may be carried out after each active metal is impregnated separately. Succession: Calcination produces a catalyst containing an active metal in its oxide form. The preferred polymerization catalyst of the present invention has a non-crystalline vermiculite-alumina substrate which is impregnated with 5 to 15% by weight and is in the form of an extrudate of 3·175 mm (〇125 inches) and has a density of 〇. .45 to 0.65 g/ml. Also included are metals incorporated into the support by other means such as ion exchange and co-milling. A co-gelatinized vermiculite-alumina carrier made by Ji Tian's oil-drop method (which allows the use of a carrier in the form of a large sphere): for example, 'as an oxidized sol system It is combined with an acidified water glass solution as a source of Shishi stone, and the mixture is further compounded (for example, 'urea, hexamethylenetetramine or a mixture thereof). Rotate the disc freely, and arrange the mixture still below the gelation temperature at the gelation temperature, &, in the secret, in the passage,... The mixture is dispersed as a droplet... It is better to form a spherical gel between the phases. By the following method: 匍 Sun / Emulsified Alumina gel dry or deionized W oxidized granules and - amount processed and formed 7 ° and 'add sufficient hydrochloric acid to digest - part of aluminum metal and form the desired sol / Caused by the metality of the file. The heart rate is the reflux temperature of the mixture 147046.doc 201040251 and is washed with water. Proper gelation of the mixture in the oil bath and subsequent gelation of the gel ball is not easy to accomplish at less than 48.9 ° C (120 ° F), and at 98.9 C (210 F), rapid gas emission easily ruptures the sphere and Weakened. Using a higher temperature often improves the results by maintaining sufficient superatmospheric pressure to maintain water in the liquid phase during the forming and curing steps. If the gel particles are aged under superatmospheric pressure, the alkaline curing step is not required. ◎ The ball system is washed with water, preferably with a small amount of ammonium hydroxide and/or water. After washing, dry at a temperature of 93.3 ° C (200 ° F) to 3 15 ° C (600 ° F) for 6 to 24 hours or longer, and then at a temperature of 426.67 ° C (800 to 760 ° C (140 (TF Calcined for 2 to 12 hours or longer. The Group VIII and Group VIB components are comprised of a co-gelatinized vermiculite-alumina carrier material by any suitable co-impregnation technique. The support material may be immersed, impregnated or suspended, or immersed in an aqueous impregnation solution containing a soluble νιπ family salt and a soluble Group VIB salt. A suitable hydrazine method involves immersing the support material in the impregnation solution, and in a rotary form. Evaporate to dryness in a steam dryer. The concentration of the impregnation solution should be such that the atomic ratio of the recorded catalyst plus the enthalpy of the final catalyst is 〇.1 to 〇.3. The method comprises immersing the support material in an aqueous impregnation solution at room temperature until the solution completely penetrates the support. After absorbing the impregnation solution, the support drains the free surface liquid and is dried in a moving belt calciner. The catalyst complex is usually at a temperature of 9 3 · 31 (2 〇〇 before calcination) Drying to 260 C (500 F) for 1 to 1 hour. According to the present invention, the calcination is carried out in an oxidizing gas at a temperature of 371. (: (700 卞) to 650 \: (1200 Τ). Doc •19- 201040251 Other gases containing molecular oxygen can be used, but the oxidizing gas is suitable for air. Another suitable catalyst is impregnated with 〇5 to 15 weights. / nickel and bismuth to 12% by weight Tungsten oil-treated vermiculite-alumina spherical carrier with a diameter of 3175 mm (0.125 inch). Other suitable methods of metal incorporation may be considered. Suitable densities for other catalysts may range from 0.60 and 0.70 g/ The dilute ethylene feed can be contacted with the polymerization catalyst at a temperature of 2 〇〇 t3 & 4 〇 (rc). The reaction mainly occurs in the ethylene-based gas phase of GHSV 50 to 1000 hr-1. Surprisingly, it has been found that despite the presence of impurities in the feedstock which poison the catalyst and thin the ethylene, at least 4% by weight and at most 75 weight percent of the ethylene in the feed gas stream are converted to heavier hydrocarbons. Ethylene is first polymerized on the catalyst to form heavier olefins. Some heavier olefins can Cyclization on the catalyst' and in the presence of hydrogen will promote the conversion of these olefins into chain-smoke, which are hydrocarbons heavier than ethylene. Although the raw material is impure, the catalyst remains stable, but it can Regeneration in inactivation. Suitable regeneration conditions include, for example, placing the catalyst in situ at 5 Torr. (: treatment in hot air for 3 hours. Activity and selectivity of the regenerated catalyst and fresh catalyst </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;兮 ......: For the early round, the gaseous flow is taken from the reactor: I 162 is contained in the downstream and the oligo-polymerization reverse tower top line 丨64 contains light gases (such as argon, ethane, unreacted The off-gas stream of olefins and light impurities can be transported to combustion unit 166 to produce a stream in the g-line 167. Or 147046.doc -20· 201040251 The gaseous product in the & top line 164 can be burned to ignite the heater (not visible) and/or to provide a source of fuel gas to the gas turbine (no display) to = electricity ★ The top line 164 is connected upstream to the combustion unit 166. The bottoms of the liquid containing heavier hydrocarbons from the concentrating knife 162 line 168 are lowered to the valve' and recycled back to the product separation section 9〇. The recirculation line 168 is downstream connected to the bottom residue 169 of the polymerization separator 162. Thus, the main column 92 is connected downstream of the upstream and upstream of the oligopolymerization reactor to the bottoms stream preferably through the recirculation line! 68 Follow % to the main column 92 between the heavy naphtha outlet 96a and the light cycle oil outlet 95a. Alternatively, a light cycle oil line 95 or a heavy naphtha line 96 is fed from a recycle line 168. The recycle line is connected downstream with the oligomerization reactor 156 = and upstream to the main column 92. Alternatively, the oligopolymerization product in line 16 or 168 may or may not be saturated and transported to a fuel tank which does not need to be recycled to the product separation zone 9 实施 [Embodiment] 用途 The use of the present invention can be demonstrated by the following example . Example 1 Using the above-described process for other catalysts of the present invention, nickel and tungsten supported on a spherical matrix of an amorphous vermiculite-alumina oil droplet were synthesized. The metal comprises 1.5% by weight of nickel and η% by weight of tungsten of the catalyst. The spherical substrates have a diameter of 3.1 75 mm. The catalyst has a ratio of vermiculite to alumina of 3 ́s 0.641 g/mL and a surface area of 371 m2/g. Example 2 Extrusion of amorphous state vermiculite-alumina synthesis system will be amorphous 矽I47046.doc -21 - 201040251 stone-oxidation Ming (the ratio of vermiculite to alumina provided by CCIC is 2.6) The pseudo-British stone provided under the trade name Catapal is a combination of 85- to -15 by weight. The s-Hui dynasty stone is used first; after the g-acid acid is peptized, it is mixed with the non-crystalline Shi Xishi _ Oxidation. A surfactant having the brand name Antarox and water sufficient to moisturize the granules are added to the mixture. The catalyst mass was extruded from a 1.59 mm opening in a cylindrical die plate and calcined at 550 ° C after being divided into segments. The final catalyst consisted of 85% by weight vermiculite-alumina and cerium 5% by weight alumina. The vermiculite to alumina ratio was 1.92 and the surface area was 268 m2/g. Example 3 3.37 g of Ni (N〇3V6H2 〇 was dissolved in 32. 〇 8 g of deionized water. The nickel solution was added in four portions and violently oscillated between additions to make the nickel solution and the extruded amorphous state of Example 2. Vermiculite_alumina contact. A light green extrudate is formed. Then, the extrudate is dried at 1HTC for 3 hours, then heated to 500 °C at 2<t/min for calcination and maintained at 50{rc first After 3 hours, it was cooled to room temperature, and the nickel metal was converted into an oxide form. The light gray extrudate was found to contain 1.5% by weight of nickel. Example 4 A zeolite sample system having a ratio of vermiculite to alumina of 40. Purchased from Ze〇lyst C〇rP〇rati〇I^ The MTT zeolite is combined with pseudo-acre and first extruded through a 3.175 opening in a cylindrical form and then calcined to 55〇〇c. It consists of 80% by weight of MTT zeolite and 2% by weight of alumina. Example 5 - at 280. (:, 6,895 kPa 〇〇〇〇 psig), 〇 ghsv (olefin gas hourly rate), at 10 mL catalyst Fixed bed operation test = 147046.doc 201040251 Example 1 Catalyst effect on olefin oligomerization. The feed is 3〇 Weight % C2H4 and 7〇 weight % CH4. The results are shown in Table i. Example 6
在 28(TC ' 6,895 kPa (1_ psig)、586 0GHSV、在 1〇 mL 觸媒上的固定床操作中，測試實例2觸 •作用。該進料由23重量％C2H4、14重量％C2H6= = CH4、13重量％ h2、13重量％ N2、丄重量％ c〇、i 5重量％ 〇 C〇2、10 wPpm HJ組成並在進入募聚合反應前，在25t 及3,447 kPa (500 psig)下經過水蒸氣飽和。結果示於表工及 圖2中。 實例7In a fixed bed operation of 28 (TC ' 6,895 kPa (1 psig), 586 0 GHSV, on 1 〇 mL of catalyst, Test Example 2 touched. The feed was 23% by weight C2H4, 14% by weight C2H6 = = CH4, 13% by weight h2, 13% by weight N2, 丄% by weight c〇, i 5% by weight 〇C〇2, 10 wPpm HJ composition and passed through 25t and 3,447 kPa (500 psig) before entering the polymerization process The water vapor was saturated. The results are shown in the table and in Figure 2. Example 7
在 280。(：、6,895 kPa (1000 psig)、586 OGHSV、在 1〇 mL 觸媒上的固定床操作中，測試實例3觸媒對烯烴寡聚合之 作用。該進料由23重量％ QH4、14重量％ c2h6、35重量％ CH4 13 重 a： °/〇 H2、13 重里 ％ N2、1 重量 ％ c〇、1.5 重量 ％ 〇 C〇2、10 wPPm H2S 組成並先在 25°c 及 3,447 kPa (500 psig) 下經過水蒸氣飽和後，再進行寡聚合反應。結果示於表工 及圖2中。在操作物流的27至44小時期間，亦將i ppm Μ% " 加至原料中。發現在轉化率或選擇性中無變化。 •實例8 除了在原料中的Hj濃度改為50 wppm而不是1〇 wppm之 外’重複實例7之實驗。結果示於表I及圖2中。 圖2係實例6至8的C#4轉化率相對於物流之操作時間之 曲線。依據乙烯轉化率，實例3的在非晶體態矽石_氡化鋁 147046.doc -23- 201040251 觸媒上之鎳比實例2之矽石-氧化鋁基質表現出較好的轉化 率。實例2及3之觸媒受到原料雜質的影響亦很小。 實例9At 280. (:, 6,895 kPa (1000 psig), 586 OGHSV, in a fixed bed operation on a 1 〇 mL catalyst, Test Example 3 Catalyst for olefin oligomerization. The feed was 23% by weight QH4, 14% by weight C2h6, 35wt% CH4 13 Weight a: °/〇H2, 13% by weight N2, 1% by weight c〇, 1.5% by weight 〇C〇2, 10 wPPm H2S Composition and first at 25°C and 3,447 kPa (500 psig) After the water vapor is saturated, the oligomerization reaction is carried out. The results are shown in the table and in Figure 2. During the 27 to 44 hours of the operation of the stream, i ppm Μ% " is also added to the raw material. There was no change in the rate or selectivity. • Example 8 The experiment of Example 7 was repeated except that the Hj concentration in the raw material was changed to 50 wppm instead of 1 〇 wppm. The results are shown in Table I and Figure 2. Figure 2 is an example. The curve of C#4 conversion rate of 6 to 8 with respect to the operation time of the stream. According to the ethylene conversion rate, the nickel ratio of the catalyst in the amorphous state 矽石_氡化铝147046.doc -23- 201040251 according to Example 3 The vermiculite-alumina matrix of 2 exhibited better conversion. The catalysts of Examples 2 and 3 were affected by raw material impurities. Also small. Example 9
在280 C、6,895 kPa (1〇〇〇 psig)、586 〇GHSV、在 1〇 mL 觸媒上的固定床操作中，測試實例4觸媒對烯烴寡聚合之 作用。δ亥原料由23重量％ C：2H4、14重量。/〇 C2H6、3 5重量％ CH4、13 重量 ％ H2、13 重量 ％ n2、1 重量 ％ c〇、1 · 5 重量 ％ c〇2、ίο wppm h2s組成並先在kPa (5〇〇 psig) 下經過水蒸氣飽和後，再進行募聚合反應。結果示於表工 及圖3中。 圖3係實例9的QH4轉化率相對於物流之操作時間之曲線 圖，其顯示，雜質可使實例4之MTT沸石觸媒中毒的作 用。反應20小時後，轉化率降至低於1〇重量％，而來自實 例3之觸媒在實例7及8中的轉化率仍維持在約6〇重量％。 實例10 在 280。(：、6,895 kPa (1〇〇〇 psig)、613 〇GHSV、在⑺虹 觸媒上的固定床操作中，測試實例4觸媒對 m 作用。該原料由3。重一及7。重量％叫二 作21小時時，加入氫氣，以獲得由27重量％ c^4、63重^ % CHU及1〇重量％ Ha組成的原料。在操作牦小時時，添7 含500 wPpm Nh3的H2，獲得含27重量％ c2H4 ' 63重、力曰口 %CH4、1〇重量％ Hj5〇 wppm丽3的原蛀 置 及圖4中。 、、，。果不於表ί 圖4係實例⑺的。^轉化率相對於物流之操作 Τ间之曲 147046.doc •24· 201040251 2圖，其顯示Η,及NH3雜質對實例42MTT沸石觸媒的影 響。可參見圖3，在操作20小時的原料中引入氫氣後，乙 烯轉化率即下降。此外’在操作45小時時，引入氨後，乙 稀轉化率明顯地迅速下降。The effect of the catalyst of Example 4 on olefin oligomerization was tested in a fixed bed operation at 280 C, 6,895 kPa (1 〇〇〇 psig), 586 〇 GHSV, on a 1 〇 mL catalyst. The raw material of δH is composed of 23% by weight of C: 2H4 and 14 parts by weight. /〇C2H6, 3 5 wt% CH4, 13 wt% H2, 13 wt% n2, 1 wt% c〇, 1 · 5 wt% c〇2, ίο wppm h2s composition and first at kPa (5 〇〇 psig) After the water vapor is saturated, the polymerization reaction is carried out. The results are shown in the table and in Figure 3. Figure 3 is a graph of QH4 conversion for Example 9 versus run time for the stream showing the effect of impurities on the MTT zeolite catalyst poisoning of Example 4. After 20 hours of reaction, the conversion was reduced to less than 1% by weight, while the conversion of the catalyst from Example 3 in Examples 7 and 8 was maintained at about 6% by weight. Example 10 is at 280. (:, 6,895 kPa (1〇〇〇psig), 613 〇GHSV, in the fixed bed operation on the (7) rainbow catalyst, test example 4 catalyst acts on m. The raw material is 3. Weight 1 and 7. Weight% When the two were used for 21 hours, hydrogen was added to obtain a raw material consisting of 27% by weight of c^4, 63% by weight of CHU and 1% by weight of Ha. At the hour of operation, 7 was added with 500 wPpm Nh3 of H2. The original device containing 27% by weight of c2H4 '63 weight, the force of the mouth %CH4, 1% by weight of Hj5〇wppm 3 was obtained and in Fig. 4. Fig. 4 is not shown in Fig. 4 is the example (7). ^ Conversion rate vs. logistics operation 147 之 147046.doc • 24· 201040251 2, which shows the effect of ruthenium and NH3 impurities on the example 42MTT zeolite catalyst. See Figure 3 for 20 hours of operation. After the introduction of hydrogen, the ethylene conversion rate decreased. In addition, after the introduction of ammonia at 45 hours of operation, the conversion of ethylene significantly decreased rapidly.
〇 實例11 八氨程序升溫脫附測試（氨TPD)包括··首先在流速100毫升/ 鐘之a 20體積百分率氧氣之氦氣環境中，將毫克觸 媒樣品依rc/分鐘之速率加熱至55(rc。維持一個小時 & ’使用氦氣沖洗該系統15分鐘，纟將樣品冷卻至 15代。然後，以4〇毫升/分鐘含氨之氦氣脈衝使該樣品飽 和。氨之總使用量大幅超過需要的數量，以使所有樣品上 ㈣位點飽和。利用40毫升/分鐘的氦氣清洗該樣品㈧、 時’以移除物理性吸附的氨。利用氦氣連續清洗，使溫度 依lot/分鐘之素率升至最終溫度60(rc。使用標準導熱檢 147046.doc -25- 201040251 測器監測脫附的氨數量。積分整合決定氨的總量。 由脫附的氨總量對樣品重量之比例得到總酸度。如本文 中使用的總酸度數值係以每克乾樣品中氨的毫莫耳單位表 示。對稀乙烯流之寡聚合具有活性的觸媒係酸性，其由氨 TPD決定的酸度為至少〇 15，及較佳至少〇 25。 在溫度達到300。(：前，從樣品中脫附的氨總量對樣品乾 重之比例得到低溫峰值。如本文中使用的低溫峰值係以每 克乾樣品中的氨毫莫耳單位表示。對稀乙烯流之募聚合具 有活性的觸媒具有低溫峰值’由氨TpD決定其低溫峰值為 至少〇·〇5 ’及較佳為至少〇 〇6。 ‘ 由低溫峰值對總酸度之比例得到無單位之比值，稱為低 溫酸度比。可抵抗稀乙烯流中原料雜質且對稀乙烯流之寡 聚合具有活性的觸媒具有藉由氨TpD決定的至少⑶，適 宜至少0.2，及較佳大於〇25之低溫酸度比。 觸媒 實例1 總酸度，奎豈五十 ~0323 _，亳莫耳/g οΤΓ^ -低溫酸度比 實例2 0.285 〇 〇〇9 — ' 0.36 實例3 0.264 nns/i ~~~~ L" 0.32 ~ 寶例4 -----η Μη 0.32~ — 一 ~—----- 0.12 ^例中可看出’衫性觸媒受到原科雜質影響而對〔 稀轉化之效率大幅下降，而本發明之觸媒儘管原 典型催化毒物之雜質，但是仍為 取' 本發明之觸媒之乙烯韓化聿心± 烯春聚合觸媒。 重量％及^ _4G重量％，典— 董置/ό及較佳7〇重量％以上。 147046.doc -26· 201040251 右未再it纟洋細說明，咸信熟習此項技術者可利用先 f的描述在最大限度上利用本發明。因此，先前較佳的特 疋只施例僅係闡述性，且在任何方面不對揭示内容進行限 制。 在上文中，除非另外指示，所有溫度皆以攝氏度表示， • 且所有份量及百分比係以重量計。 從上文描述中’熟習此項技術者可輕易地確定本發明之 0 基本特徵，及在不背離其精神及範圍時，可對本發明做出 各種改變及修改以使其適應各種用途及條件。 【圖式簡單說明】 圖1係FCC單元及FCC產物回收系統之示意圖； 圖2係實例6至8的乙烯轉化率相對於物流之操作時間之 曲線圖； 圖3係實例9的乙烯轉化率相對於物流之操作時間之曲線 圖；及 ◎ 圖4係來自實例10的乙稀轉化率相對於物流之操作時間 之曲線圖。 【主要元件符號說明】 6 煉油廠集合體 10 FCC單元區段 12 FCC反應器 14 觸媒反應器 16 分流器 18 再生觸媒豎管 147046.doc 201040251 20 立管 22 反應器 24 流化管線 26 初級分離器 28 旋風分離器 31 產物出口 32 管線 34 汽提區段 36 消耗觸媒豎管 38 空氣分流器 40 燃燒器立管 42 選別器 44 旋風分離器 46 旋風分離器 47 廢氣出口 48 廢氣管線 90 產物回收區段 92 分餾管柱 93 管線 94 管線 95 管線 95a 出口 96 管線 96a 出口 147046.doc -28 201040251〇Example 11 Octa-Ammonia Temperature Desorption Test (Ammonia TPD) includes: First, the milligram catalyst sample is heated to 55 at a rate of rc/min in a helium atmosphere of a flow rate of 100 ml/h. (rc. Maintain for one hour & 'Use the helium gas to flush the system for 15 minutes, then cool the sample to 15 generations. Then, saturate the sample with a 4 〇 ml/min helium-containing helium pulse. Total ammonia usage Substantially exceed the required amount to saturate all (4) sites on the sample. Clean the sample (8) with 40 ml/min of helium, to remove the physically adsorbed ammonia. Use helium to clean continuously, so that the temperature depends on lot The rate of /min is raised to a final temperature of 60 (rc. The amount of ammonia desorbed is monitored using a standard thermal conductivity test 147046.doc -25- 201040251. The integral integration determines the total amount of ammonia. The ratio of the weight gives the total acidity. The total acidity value as used herein is expressed in millimole units of ammonia per gram of dry sample. The catalyzed acidity of the oligomeric polymerization of the dilute ethylene stream is determined by the ammonia TPD. Acidity is at least 〇15, and preferably at least 〇25. At a temperature of 300. (Before, the ratio of the total amount of ammonia desorbed from the sample to the dry weight of the sample gives a low temperature peak. The low temperature peak as used herein is per gram of dry The ammonia millimolar unit in the sample indicates that the catalyst having activity for the polymerization of the dilute ethylene stream has a low temperature peak 'determined by the ammonia TpD whose peak temperature is at least 〇·〇5' and preferably at least 〇〇6. From the ratio of low temperature peak to total acidity, the unitless ratio is obtained, which is called low temperature acidity ratio. The catalyst which is resistant to raw material impurities in the dilute ethylene stream and active to the oligomerization of the dilute ethylene stream has at least (3) determined by ammonia TpD. Suitable for a low temperature acidity ratio of at least 0.2, and preferably greater than 〇 25. Catalyst Example 1 Total acidity, Kudzu 50~0323 _, 亳莫耳/g οΤΓ^ - Low temperature acidity ratio Example 2 0.285 〇〇〇9 — '0.36 Example 3 0.264 nns/i ~~~~ L" 0.32 ~ Bao Example 4 -----η Μη 0.32~ — One ~—----- 0.12 ^ In the example, it can be seen that 'shirt-like catalyst is affected The influence of the original impurities on the [dilute conversion efficiency is greatly reduced, and the catalyst of the present invention The original catalytic poison of the original toxicant, but still takes the ethylene catalyst of the catalyst of the invention, the olefinic polymerization catalyst, the weight percent and ^ _4G weight percent, the code - Dong set / ό and preferably 7 〇 wt% Above. 147046.doc -26· 201040251 The right is not to be explained in detail. Those skilled in the art can use the description of the first f to maximize the use of the present invention. Therefore, the prior preferred features are only examples. It is merely illustrative and does not limit the disclosure in any way. In the above, all temperatures are expressed in degrees Celsius unless otherwise indicated, and all parts and percentages are by weight. From the above description, one skilled in the art can readily determine the basic characteristics of the present invention, and various changes and modifications can be made to the various uses and conditions without departing from the spirit and scope thereof. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of an FCC unit and an FCC product recovery system; Figure 2 is a graph of ethylene conversion of Examples 6 to 8 versus operating time of the stream; Figure 3 is a graph showing the relative ethylene conversion of Example 9. A graph of the operating time of the stream; and ◎ Figure 4 is a graph of the ethylene conversion rate from Example 10 versus the operating time of the stream. [Main component symbol description] 6 Refinery complex 10 FCC unit section 12 FCC reactor 14 Catalytic reactor 16 Splitter 18 Regeneration catalyst riser 147046.doc 201040251 20 Standpipe 22 Reactor 24 Fluidization line 26 Primary Separator 28 Cyclone separator 31 Product outlet 32 Line 34 Stripping section 36 Catalyst riser 38 Air splitter 40 Burner riser 42 Separator 44 Cyclone separator 46 Cyclone separator 47 Exhaust gas outlet 48 Exhaust line 90 Product Recovery section 92 Fractionation column 93 Line 94 Line 95 Line 95a Outlet 96 Line 96a Outlet 147046.doc -28 201040251
97 塔頂管線 99 主管柱接收器 101 管線 102 管線 104 壓縮器 106 管線 107 管線 108 塔頂管線 110 高壓接收器 112 管線 114 初級吸收器 116 管線 118 二級吸收器 119 管線 120 蒸汽回收區段 121 管線 122 管線 124 管線 126 汽提塔 128 管線 130 脫丁烷塔管柱 132 管線 134 管線 140 吸收器單元 147046.doc •29 201040251 142 管線 143 管線 144 管線 145 管線 146 清洗單元 147 管線 148 管線 150 保護床 151 管線 152 壓縮器 154 管線 156 募聚合反應器 158 固定催化劑床 160 管線 162 寡聚合分離器 164 塔頂管線 166 燃燒單元 167 管線 168 再循環管線 169 底部殘留物 147046.doc •30-97 overhead line 99 main column receiver 101 line 102 line 104 compressor 106 line 107 line 108 overhead line 110 high pressure receiver 112 line 114 primary absorber 116 line 118 secondary absorber 119 line 120 steam recovery section 121 122 Line 124 Line 126 Stripper 128 Line 130 Debutanizer Column 132 Line 134 Line 140 Absorber Unit 147046.doc • 29 201040251 142 Line 143 Line 144 Line 145 Line 146 Cleaning Unit 147 Line 148 Line 150 Protection Bed 151 Line 152 Compressor 154 Line 156 Polymerization Reactor 158 Fixed Catalyst Bed 160 Line 162 Oligomeric Separator 164 Column Top Line 166 Combustion Unit 167 Line 168 Recirculation Line 169 Bottom Residue 147046.doc • 30-