TW399092B

TW399092B - Layered catalyst system for lube oil hydroconversion

Info

Publication number: TW399092B
Application number: TW087111496A
Authority: TW
Inventors: James N Ziemer; Dennis J O'rear; Donald S Santilli
Original assignee: Chevron Usa Inc
Priority date: 1996-07-15
Filing date: 1998-07-15
Publication date: 2000-07-21
Also published as: EA199900108A1; CA2259539A1; WO1998002503A1; AU3664997A; CZ9699A3; AU724363B2; TR199900097T2; HUP0004280A3; KR20000023803A; EP0912660A1; PL331037A1; HUP0004280A2; JP2000515185A; EA001619B1; BR9710326A

Abstract

In a lube oil hydrocarbon processing process involving sequential steps of hydrotreating to remove heteroatoms and at least a portion of the aromatics followed by hydrotreating/hydrocracking for aromatic saturation, isomerization and VI upgrade, followed by hydroisomerization for wax removal and finally hydrofinishing for lube oil stability, the improved process for second stage hydrocracking which comprises : a second catalyst layer on top of a first catalyst layer in said reactor said second catalyst selected from the group consisting of noble metal amorphous catalysts, noble metal hydrocracking catalysts, or combinations thereof and wherein said first and second catalyst combination achieves a longer catalyst life with higher activity and higher yields at a constant VI for the base lube oil fabrication than solely a reactor charged with solely said first catalyst.

Description

經濟部中央標準局員工消費合作社印製 -广 I ----------τη ι„ jj, 第87111496號專利申ΐ#正 g ，1 說明書修正頁(S9年4月W Μ @7 五、發明説明（6 ) 現，其在催化劑床區域可包含多數不同催化劑以最佳化最終及給定基油產品流。提供增加催化劑活性主要利益之非晶態催化劑貴金屬的組合系統，其導致更長催化劑壽命，然而下面區域催化脫蠟進料的蠟質部分以提供黏度指數驟增及極大化產率兩者至整體產品流。附一 5 石油進料 140 催化脫蠟反應區 10 蒸餾塔 141 催化脫蠟反應器 100 系列為輕質進料 151 氫化作用反應器 102 輕餾出液部份 152 脫堪輕油產品 110 加氫裂解反應區 154 富氫氣體流 111 加氫裂解反應器 156. 富氫氣體流 120 第一分離區 160 氫化作用反應區 122 純化富氫氣體流 162 流出物 124 輕堪質氫化裂解物 170 分離區 128 輕蝶質氫化裂解物 172 含氫氣體流 130 蒸餾塔 174 輕質潤滑油基料 132 堪質油部份 200 系列為重質進料 134 蠟質油部份 202 重餾出液部份 136 蠟質油部份 274 重質潤滑油基料 -9- 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） ----------裝 I-^-----訂------綵 (請先閱讀背面之注意事項再填寫本頁) 五、發明説明（ A7 B7 曼_明領域本發月係原★之力口氫觸媒轉化。比較明確言之，本發明係製造潤滑油基料之層狀催化劑系統。發明背景 -成 a '由爲石油基油及罐裝添加劑之主要組成。基油係由原油經由多數如蒸餾、加氫裂解、加氫處理、催化脱虫f及類似方法煉製而成。這些方法所得之基油先質需要 =處理以生產成品基油。&製者纟生產基油時意欲獲得最 :可旎產率，但同時保持油之黏度指數。對蠟質原油維持问產率爲特別困難的問題。一解決方案爲溶劑脱蠟化油中之蠟貝郅份。然而，此容易降低產率在一定黏度指數下之產率。此產率議題已指出溶劑萃取後經催化脱蠟而由蠟質基油中生產潤滑油基料。然而除去蠟最後.微量之脱蠟步驟會影響傾點及濁點而罰降產率。因此亟欲在一定黏度指數下最佳化產率之方法。在潤滑塗油製造中，催化脱蠟或氫化處理、或加氫裂解爲在反應器内不連續區域或在不連續反應器内進行。此程序爲昂貴的，且增加整體方法或給定反應器之複雜性。因此亟欲存在催化劑層積系統，其中一種類型或種類催化劑係層覆於其後催化劑層之。此種配置提供較快順序處理及車父緊·凑設計而且簡單化方法和反應器内構。發明概述本發明係指製備潤滑油基料之方法，其包括使用加氫異構化脱蠟催化劑將蠟質加氫裂解石油予以脱蠟。 (請先閱讀背面之注意事項再填寫本頁) Τ ___ *Tu i 第87111496號專利兮說明書修正頁(89年 ί、 4.^ A7 B7 五、發明説明（）圖面說明圖1為本發明較優整合方法之流程圖。圖2展示本層狀脫蠟催化劑系統產率之利益。圖3展示本層狀脫蠟催化劑系統黏度指數的利益。圖4展示層狀脫蠟催化劑系統對觀察得催化活性的效果。發明詳述本發明係指製備潤滑油基料中脫蠟蠟質進料之層狀催化劑。當與傳統應用單一脫蠟催化劑之脫蠟方法相比時，層狀系統提供高黏度指數脫蠟油之較高產率人第二催化劑層包括貴金屬氫化作用成分，提供氫化處理使芳族飽和化二鏈烷烴加氫異構化。至少第二催化劑層流出物之部分與包含異構脫蠟催化劑之第一催化劑層裡氫接觸，其藉著加氫異構化裂解、甚或轉化油中蟻質分子成非壤質型以減少壤質油之傾點。經濟部中央標準局負工消費合作社印裝 (請先閲讀背面之注意事項再填寫本頁) 可依本發明處理之進料包括：油類其通常具較高傾點，其需要減少到較低傾點。於此適用之該石油進料可選自包 ;下列族群中.#原油、具正常潍點高於約⑽。c之石油餘出液、氣體油類和真空氣體油類、大氣壓蒸餾法之餾餘油邵份、溶劑-去瀝青石油殘餘物、頁岩石油、循環油、石油 -9a - 本紙俵尺度糾中國國家核準（CNS ) A4胁（21GX297公釐 A7 ______ B7 五、發明説明（2 ) 本發明再指製備潤滑油基料之脱蠟方法及層狀脱蠟催化劑系統'。層狀催化劑系統包含催化劑，其具氫化處理反應之催化性質、包括芳族飽和化及黏度指數增加、而具最小之分子量降低，及異構脱蠟催化劑，其具有蠟加氫異構化而降低傾點之催化性質。比較明確言之地，本發明提供層狀催化劑系統，其中第 —層催化劑預處理潤滑油基料，而第二層完成蠟質進料之脱壤以維持高的產率而無犧牲黏度指數，同時具能力使用向催化活性催化劑以加速方法或在省能源低溫下操作反應器。如此在潤滑油烴類處理方法中涉及順序步驟：氫化處理以除去異類原子及至少一部分芳族，然後氫化處理/加氫裂解以將芳族化合物飽和化、異構化及黏度指數升級，然後加氫異構化以移除蠟類及最後加氫完成以獲得潤滑油穩定性，第二階段加氫裂解的改良方法包含：反應器裡的第一催化劑及其上層覆之第二催化劑，該第一催化劑包括異構脱蠟催化劑·，及於該反應器中第一催化劑層上之第二催化劑層，該第二催化劑選自包含下列族群中：貴金屬非晶態催化劑、貴金屬加氫裂解催化劑、或其組合物，且其中該第一及第二催化劑组合物，在基礎潤滑油製造時，比起單_反應器裝以單一之該第一催化劑而言，在給定黏度指數下，達成較長催化劑壽命及較高活性和較高產率。、在較優方法中，蠟質油與在氧化物支載基質上包括音金屬氫化作用成分之氫化處理催化劑之氫接觸。氫化處理催 -5- 本纸张尺度適川中囚囤家行碑（（，NS ) 規格（2^97公楚j —_Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs-广 I ---------- τη ι „jj, No. 87111496 Patent Application # 正 g, 1 Revision Sheet (S9 Apr. W Μ @ 7 V. Description of the invention (6) Now, it can contain many different catalysts in the catalyst bed area to optimize the final and a given base oil product stream. A combination system of amorphous catalyst precious metals that provides the main benefit of increasing catalyst activity, which leads to Longer catalyst life, however, the waxy portion of the dewaxing feed is catalyzed in the lower zone to provide both a sudden increase in viscosity index and maximized yield to the overall product stream. Attached 5 Petroleum Feed 140 Catalytic Dewaxing Reaction Zone 10 Distillation Tower 141 Catalytic dewaxing reactor 100 series is light feed 151 Hydrogenation reactor 102 Light distillate fraction 152 Light oil product 110 Hydrocracking reaction zone 154 Hydrogen-rich gas stream 111 Hydrocracking reactor 156. Hydrogen-rich gas stream 120 First separation zone 160 Hydrogenation reaction zone 122 Purified hydrogen-rich gas stream 162 Effluent 124 Light hydrogenated pyrolysate 170 Separation zone 128 Light light hydrogenated pyrolysate 172 Hydrogen-containing gas stream 130 Distillation column 174 Light lubricating oil base 132 Corrosion oil part 200 series is heavy feed 134 Wax oil part 202 Heavy distillation liquid part 136 Wax oil part 274 Heavy lubricating oil base-9 -This paper size adopts Chinese National Standard (CNS) A4 specification (210X297 mm) ---------- install I-^ ----- order ------ color (please read first Note on the back, please fill in this page again.) V. Description of the invention (A7 B7 Mann_Ming field is the original ★ of the original hydrogen catalyst conversion. More specifically, the present invention is a layered lubricant base Catalyst system. Background of the invention-Cheng a 'is mainly composed of petroleum base oil and canned additives. Base oil is made from crude oil through most processes such as distillation, hydrocracking, hydrotreating, catalytic deworming and similar methods. The base oil precursors obtained by these methods need = processing to produce finished base oils. &Amp; Producers want to get the most when producing base oils: the yield can be achieved, but at the same time maintain the viscosity index of the oil. Maintain for waxy crude oil Asking for yield is a particularly difficult problem. One solution is the wax content in solvent dewaxed oil. However, This easily reduces the yield at a certain viscosity index. This yield issue has pointed out that after the solvent extraction, catalytic dewaxing is used to produce a lubricating oil base from a waxy base oil. However, the wax is finally removed. A small amount of dewaxing step It will affect the pour point and cloud point and reduce the yield. Therefore, it is urgent to optimize the yield method under a certain viscosity index. In the manufacture of lubricating oil, catalytic dewaxing or hydrogenation treatment, or hydrocracking to react Discontinuous areas within the reactor or within a discontinuous reactor. This procedure is expensive and adds complexity to the overall process or a given reactor. Therefore, it is desirable to have a catalyst layering system in which one type or kind of catalyst system layer is coated on the subsequent catalyst layer. This configuration provides faster sequential processing and compact design, and simplifies the method and reactor internal structure. SUMMARY OF THE INVENTION The present invention refers to a method for preparing a lubricating oil base, which includes dewaxing a waxy hydrocracked petroleum using a hydroisomerization dewaxing catalyst. (Please read the precautions on the back before filling out this page) Τ ___ * Tu i Patent No. 87111496 Revised Sheet (89 ί, 4. ^ A7 B7 V. Description of the invention () Illustration of the drawing Figure 1 is the invention Flow chart of a better integration method. Figure 2 shows the benefits of the yield of the layered dewaxing catalyst system. Figure 3 shows the benefits of the viscosity index of the layered dewaxing catalyst system. Figure 4 shows the observations of the layered dewaxing catalyst system. Effect of catalytic activity. Detailed description of the invention The present invention refers to the preparation of a layered catalyst for dewaxing waxy feed in a lubricating oil base. When compared to traditional dewaxing methods using a single dewaxing catalyst, the layered system provides a high level of Higher yield of viscosity index dewaxed oil. The second catalyst layer includes a noble metal hydrogenation component, which provides hydrogenation treatment to hydroisomerize the aromatic saturated diparaffin. At least part of the effluent of the second catalyst layer isomerized with isomerization. In the first catalyst layer of the dewaxing catalyst, hydrogen is contacted, and it is cracked by hydroisomerization, or even transforms the ant substance molecules in the oil into non-loamy type to reduce the pour point of the loamy oil. Printing for off-load consumer cooperatives (please read the notes on the back before filling out this page) The feeds that can be processed according to the present invention include: oils which usually have a higher pour point, which need to be reduced to a lower pour point. The applicable petroleum feed can be selected from the following groups: #crude oil, petroleum residues with normal Wei point higher than about ⑽.c, petroleum residual effluents, gas oils and vacuum gas oils, distillate oil from atmospheric pressure distillation Shao Fen, Solvent-Deasphalted Petroleum Residue, Shale Oil, Circulating Oil, Petroleum-9a-Paper Size Correction China National Approval (CNS) A4 threat (21GX297 mm A7 ______ B7 V. Description of the invention (2) Refers to a dewaxing method and a layered dewaxing catalyst system for preparing lubricating oil base materials. The layered catalyst system contains a catalyst that has the catalytic properties of a hydrogenation reaction, including aromatic saturation and increased viscosity index, and has the smallest molecular weight Reduction and isomerization dewaxing catalyst, which has the catalytic property of wax hydroisomerization to reduce pour point. More specifically, the present invention provides a layered catalyst system in which the first layer catalyst is pretreated and moisturized. Oil base, and the second layer completes the de-soiling of the waxy feed to maintain high yields without sacrificing the viscosity index, while having the ability to use catalytically active catalysts to accelerate the process or operate the reactor at low energy-saving temperatures. The lubricating oil hydrocarbon processing method involves sequential steps: hydrogenation treatment to remove heterogeneous atoms and at least a part of the aromatics, and then hydrogenation treatment / hydrocracking to saturate, isomerize and upgrade the viscosity index of aromatic compounds, and then hydrogenate Isomerization is accomplished by removing waxes and final hydrogenation to obtain lubricating oil stability. An improved method for the second stage of hydrocracking includes: a first catalyst in a reactor and a second catalyst overlying the first catalyst. The catalyst includes an isomerized dewaxing catalyst, and a second catalyst layer on the first catalyst layer in the reactor, the second catalyst being selected from the group consisting of a noble metal amorphous catalyst, a noble metal hydrocracking catalyst, or Its composition, and wherein the first and second catalyst compositions are manufactured with a single For the catalyst, at a given viscosity index, to achieve higher activity and a longer catalyst life and higher yields. In a preferred method, the waxy oil is contacted with hydrogen from a hydrogenation catalyst comprising a metal hydrogenation component on an oxide-supported substrate. Hydrogenation reminder -5- This paper is suitable for the prisoners in Sichuan ((, NS) specifications (2 ^ 97 公楚 j —_

In rn n HI (請先閱讀背面之注意事項再填寫本頁) A7 ________Β7 五、發明説明（3 ) 化劑床之流出物然後與異構脱蠟催化劑接觸。 - ---i 1-- -I- I - I -· n^i nil - _ \~f*I! -I - iii -i- ! - i,OJ (請先閲讀背面之注意事項再填寫本頁) 第一''層異構脱蠟催化劑包含中値孔分子篩，與其他類型脱螺_催化劑比較，調適到脱躐油之高產率，且具孔隙7工埃、最優6.5埃、或直徑更小，及具至少一個孔隙直徑大於或等於4 _ 8埃且具微晶大小不大於約〇. 5微米。催化劑特徵爲其具足夠酸性以在37CTC時至少轉換50%的十六烷，和具 40或更大之同分異構化選擇性比率，在此定義爲96Q/❶十六燒轉化率。催化劑再至少包括一個第V111族金屬。第二催化劑爲選自包含下列族群中：貴金屬覆蓋非晶態催化刎、貴金屬加氫裂解催化劑、或其組合物，其包含貴金屬選自鉑族金屬，包括鉑'鈀、鍺、釕、銥和鍊。較優鉑族金屬爲鉑、紅、或其组合物因此在較優實例中，本方法包含在氫存在之芳族化合物飽和條件下，以氫化處理催化劑接觸含少於大約100百萬分之一硫及少於約5 〇百萬分之一氮之蠟質進料而產生加氫處理過油及氣體流；及在異構化條件下，以異構脱蠟催化劑泮接觸加氫處理過油及氣體流而產生脱樣過油，其具傾點相對於虫鼠質進料傾點而言爲減少，且其中氮化處理條件爲預鱼定以維持氫化處理反應區裡的液態轉化率小於約25% 體積比。山在個別實例中，本發明係指用來製備潤滑油基料之整合俶化劑系統。在由石油進料產生多數潤g油基料之整合方法中，該方法包含： a)分開石油進料進入至少一個輕餾份流和至少一重餾份本祕尺料 ------ Α7 Β7 五、發明説明（流； b)產生至少一輕質潤滑油基料之方法，其包括： i) 在加氫裂解反應條件足以將至少硫之部分及至少氮之邵分由輕餾份流中移開下，以第一加氫裂解反應區裡之氫接觸至少一輕鶴份流，而產生至少一個壤質輕油組份，其具黏度指數相對於輕餾份流之黏度指數而言爲增加 ii) 用第一脱蠟反應區中氳接觸至少一蠟質輕油组份，該反應區包括層狀催化劑系統，其包含第一催化劑及層覆其上之第二催化劑，第一催化劑包括異構脱壤催化劑；而第二催化劑’選自包含下列族群中：貴金屬非晶態催化劑、貴金屬加氫裂解催化劑、或其組合物；及 - ill)在足以產生輕質潤滑油基料條件下在氫化作用反應區接觸至少部分第一個脱蠟反應區流出物；及 C)產生至少一重潤滑油基料之方法，其包括： 1 )在條件足以將至少硫之部分及至少氮之部分由重齒份流中移開下，以第二加氫裂解反應區裡之氫接觸土少一重餘份流’而產生至少一增質重油_組份，其具黏度指數相對於重餾份流之黏度指數而言爲增加； 11)用第二脱蠟反應區中氫接觸至少一蠟質輕油组份’該反應區包括層狀催化劑系統，、其包含第二催化劑及層覆其上之第四催化劑，第三催化劑包括異構脱螺·催化劑；而第四催化劑選自包含下列族群中：貴金 (請先閱讀背面之注意事項再填寫本頁) 訂---.· 本纸张尺度诚A中國i χ 29Ϊ^~) Α7 Β7 五、發明説明（屬非晶態催化劑、貴金屬加氫裂解催化劑、或其組合物；及 (請先閱讀背面之注意事項再填寫本頁) iii)在足以產生重質潤滑油基料條件下在氫化作用反應區接觸至少部分第二個脱蟻反應區流出物，其中產生至少一輕質潤滑油基料的方法及產生至少—個重質潤滑油基料的方法爲在平行反應序列中同時地進行。本系統比起傳統催化劑系統的一個優點爲其有效性，因本方法可用以製備如此鬲品質基油用供製造潤滑油，及特別的進料，其慣例非認知爲該基油之適當來源。訂—. 在其他因素中’本發明基於發現如果異構脱蠟催化劑之邵分在脱蠟反應區中由包括貴金屬氫化作用成分之氫化處理催化劑替換，則調適脱蠟油高產率之異構脱蠟催化劑之績效可改良。包含鉑/鈀合金氫化作用成分之氫化處理催化劑已發現特別地改催化績效。比較明確言之，吾人已經驚訝地發現，將氫化處理催化劑層增加到芳族飽和脱蠟反應區可増進催化脱蠟器之可操作性、減少無法控制放熱反應效應、且改良脱蠟油的性質。甚至更驚訝的在脱蠟反應區中包括氫化處理催化劑層，讓脱蠟前加氫裂解步驟之嚴格性減 >，而捭影響到方法中產生高品質潤滑油基料之性質二較優績效相信至少部份是因爲到氫化處理催化劑有效地除去硫和氮、打開芳香族及環狀結構、且在脱蠟之前增加蝶質油之黏度指數而損失很小甚或沒肴損失潤滑油之產率。本發明再來自製造潤滑基油催化劑床之令人驚訝的發 _____ -8- 經濟部中央標準局員工消費合作社印製 -广 I ----------τη ι„ jj, 第87111496號專利申ΐ#正 g ，1 說明書修正頁(S9年4月W Μ @7 五、發明説明（6 ) 現，其在催化劑床區域可包含多數不同催化劑以最佳化最終及給定基油產品流。提供增加催化劑活性主要利益之非晶態催化劑貴金屬的組合系統，其導致更長催化劑壽命，然而下面區域催化脫蠟進料的蠟質部分以提供黏度指數驟增及極大化產率兩者至整體產品流。附一 5 石油進料 140 催化脫蠟反應區 10 蒸餾塔 141 催化脫蠟反應器 100 系列為輕質進料 151 氫化作用反應器 102 輕餾出液部份 152 脫堪輕油產品 110 加氫裂解反應區 154 富氫氣體流 111 加氫裂解反應器 156. 富氫氣體流 120 第一分離區 160 氫化作用反應區 122 純化富氫氣體流 162 流出物 124 輕堪質氫化裂解物 170 分離區 128 輕蝶質氫化裂解物 172 含氫氣體流 130 蒸餾塔 174 輕質潤滑油基料 132 堪質油部份 200 系列為重質進料 134 蠟質油部份 202 重餾出液部份 136 蠟質油部份 274 重質潤滑油基料 -9- 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） ----------裝 I-^-----訂------綵 (請先閱讀背面之注意事項再填寫本頁) 第87111496號專利兮說明書修正頁(89年 ί、 4.^ A7 B7 五、發明説明（）圖面說明圖1為本發明較優整合方法之流程圖。圖2展示本層狀脫蠟催化劑系統產率之利益。圖3展示本層狀脫蠟催化劑系統黏度指數的利益。圖4展示層狀脫蠟催化劑系統對觀察得催化活性的效果。發明詳述本發明係指製備潤滑油基料中脫蠟蠟質進料之層狀催化劑。當與傳統應用單一脫蠟催化劑之脫蠟方法相比時，層狀系統提供高黏度指數脫蠟油之較高產率人第二催化劑層包括貴金屬氫化作用成分，提供氫化處理使芳族飽和化二鏈烷烴加氫異構化。至少第二催化劑層流出物之部分與包含異構脫蠟催化劑之第一催化劑層裡氫接觸，其藉著加氫異構化裂解、甚或轉化油中蟻質分子成非壤質型以減少壤質油之傾點。經濟部中央標準局負工消費合作社印裝 (請先閲讀背面之注意事項再填寫本頁) 可依本發明處理之進料包括：油類其通常具較高傾點，其需要減少到較低傾點。於此適用之該石油進料可選自包 ;下列族群中.#原油、具正常潍點高於約⑽。c之石油餘出液、氣體油類和真空氣體油類、大氣壓蒸餾法之餾餘油邵份、溶劑-去瀝青石油殘餘物、頁岩石油、循環油、石油 -9a - 本紙俵尺度糾中國國家核準（CNS ) A4胁（21GX297公釐 A.7 B7 五、發明説明（及沸化軟石蠟、蠟質石油進料、纳歐（ΝΑΟ、商品名）蝶、及在化學工廠方法中產生之蠟。具1 6個或更多竣原子之直鏈正-鏈烷烴爲單獨或只與些微分支鏈烷烴有時在此稱爲蠟。較優石油餾出液在正常沸點範圍由2〇〇。(：至7〇〇。(：、更優由260°C至650°C下沸騰。合適進料包括那些重餾出液，通常定義爲重直餾氣體油類及重裂解循環油類，和傳統的流體化床催化裂解進料及其部分。裂解進料可得自加熱或催化裂解各種不同之原料。進料在供應到本方法之前，可能施以氫化處理及/或加氫裂解方法。另一方面，或可再加添地，進料可能在脱蠟之前於溶劑萃取方法處理以除去芳族化合物及含疏-和含氮-分子。依本發明處理有利之典型進料㉟常具起始傾點高於约〇。(：，更通常高於約2G°C。方法之後形成產品完成後通常具傾點低於約-0 °C、更優低於約_ 1 〇°c。此處所用術語”蠟質石油進料”包括石油蠟。本發明方法所應用之進料可能是躐質進料，#包含大於約5〇%壌、甚至使是大於約90%蠟。高鏈烷烴進料i古竹具呵的傾點，通常高於約0 C。更通常南於約1 〇 °C，亦可福人、λ丄 J通合於本發明方法裡使用。孩進料可包含大於約70%鏈烷炉疋；工琰類、甚至大於約 90%鏈烷烴碳類。可使用於本發明方法之適當進料翁 . r „ 种頸外例包括蠟質餾出液進料，如氣體油類、潤滑油料、人士 »成油類和摄，如由費雪•閼法（Fischer-Tropsch )合成杏丄〜奇、向傾點聚α -烯烴、腳油類、合成蠟物質，如正常α-烯杻布& %、鬆弛蠟。脱油蠟 10 本纸浓尺度进川中國囚家掠冷（ΓΝϋ ) Λ4規格（210X297公釐 —-1--I---1 -----n τ 、-'° (請先閱讀背面之注意事項再填寫本頁) A7 五、發明説明（8 ) '—' —------ 和微微結晶壤。腳油由分開壤及油而製備。分離出之油稱作腳油i。鬆弛蠟可得自加氫裂解潤滑油或溶劑精煉潤滑油。加氬裂解爲較優，因爲該方法亦可減少氮含量到低値。使由溶劑精煉油類衍生之鬆弛竣，脱油可用以減少氣含量。視需要而定，鬆弛壞之氫化處理可進行以降低其氮含量。鬆弛蠟具非吊问黏度栺數’正常範圍在由i4〇到2〇〇，依油含量和製備蠟之起始材料而定。鬆弛蠟因此顯著地適供製備具非常高黏度指數之潤滑油，此即由約12〇到約18〇。被^層狀催化劑包含反應器裡第一催化劑和其上層覆之第二催化劑，該第一催化劑包括·異構脱蠟催化劑；及於該反應器第一催化劑層上之第二催化劑層，該第二催化劑層爲選自包含下列族群中：貴金屬非晶態催化劑、貴金屬加氫机解催化劑、或其組合物。催化劑層包含由約丄到約7〇%體積比之第二催化劑層及由約99%到約3〇%體積比之第一催化劑層。由約5%到約50〇/〇體積之第二催化劑層爲較優，且由約20到約30%體積此爲最優，剩餘爲第一催化劑層。可用於本脱蠛方法之層狀催化劑包含氫化處理催化劑，其選自包含下列族群中：貴金屬非晶態催化劑、貴金屬加氫裂解催化劑、或其組合物。有用的貴金屬包括鉑、鈀、釘、铑、锇和銥。當本發明所用之氫化處理催化劑包含至少一金屬時，其亦可能使用二或更多金屬或其化合物之組合物，如例爲金屬包含鉑和鈀兩者之一組合物。業間習知多數方法以;殿積鉑和麵金屬或其化合物至支載上，例如， -11 - 本紙張尺/^ 州巾® ( 2l0X297^t ) ---— n n n m m n -- In - - n n HI IT T 3 、T (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（9 離子交换、浸入、共沉澱作用等等。氨化，處理催化劑再包含基質材料、其爲抗溫和並他法應用之條件。基質材料中至少包含—黏合劑，例如自效界發生之黏土及無機氧化物，用以改良催化劑之抗碎強度。戰化物基質材料，其包括黏合劑，選自並間通常製備催化劑之氧化物，包括矽石、氧化鋁、氧化鎂、氧化結、氧化鈇。黏土也可使用。本發明應用較優催_0 =化物基質材料，通常由以.氧化减科製備。氧化物^ 質材料裡的石夕石和氧化銘的分配可爲均句或不均勾的，但較優爲不均勻。較優形式氧化物基質材料包含氧化銘凝膠黏合劑所組成，其分散切石：氧化銘基質材料，該形式在此處當做”非Μ支載"。域物也可包含^於氧化銘或珍石之其他耐火材料，其例如其他無機氧化物或黏土粒子’其條件爲該材料*會不利地影f最終催化劑之氨化處理活性。可能存在支載物内之其他無機氧化物可能包括但艮於_乳化鈥、氧化鎂及氧化锆或其組合物。通常石夕石_ 乳化銘將會組成至少90重量百分比且較優最高可達100重量百分比之基質#料’但不計氧化物黏合劑，而且基質材 :將包含由約5重量百分比到約7〇重量百分比之黏合劑的，且較優由約20重量百分比到約5〇重量百分比之黏合劑。黏合劑材料可能包括下列氧化物：鋁、矽、鎂、鍺、 =和锆。此氧化物與其他氧化物之组合杨亦爲有用的。氧鋁黏合劑爲較優。貴金屬非晶態催化劑包含貴金屬氫化作用成分和—非晶態（此即非結晶的）基質材料。可用於本 21 Ox 297公釐） ί 、/京------ (請先閲讀背面之注意事頃#異笔良f ) I--—- ·In rn n HI (Please read the notes on the back before filling this page) A7 ________B7 V. Description of the invention (3) The effluent of the chemical agent bed is then contacted with the isomerized dewaxing catalyst. ---- i 1-- -I- I-I-· n ^ i nil-_ \ ~ f * I! -I-iii -i-!-i, OJ (Please read the notes on the back before filling (This page) The first '' layer isomerization dewaxing catalyst contains mesoporous molecular sieves. Compared with other types of despirating catalysts, it is adapted to the high yield of deoiled oil and has a pore size of 7 Angstroms, optimal 6.5 Angstroms, or 5 微米。 Smaller diameter, and with at least one pore diameter greater than or equal to 4 -8 angstroms and with a crystallite size of not more than about 0.5 microns. The catalyst is characterized by being sufficiently acidic to convert at least 50% of hexadecane at 37 CTC and having an isomerization selectivity ratio of 40 or greater, which is defined herein as a 96Q / fluorene hexadecane conversion. The catalyst further includes at least one Group V111 metal. The second catalyst is selected from the group consisting of a noble metal-covered amorphous rhenium, a noble metal hydrocracking catalyst, or a combination thereof comprising a noble metal selected from the platinum group metals, including platinum'palladium, germanium, ruthenium, iridium, and chain. The preferred platinum group metal is platinum, red, or a combination thereof. Therefore, in a preferred embodiment, the method includes contacting a hydrogenation catalyst with less than about one part per million in the presence of a saturated aromatic compound in the presence of hydrogen. Sulfur and waxy feeds of less than about 50 parts per million nitrogen to produce hydrotreated oils and gas streams; and contacting hydrotreated oils with isomerized dewaxing catalysts 异构 under isomerization conditions Degassing and oil generation caused by gas and gas flow, the pour point is reduced relative to the pour point of zoological feed, and the nitriding treatment conditions are pre-determined to maintain the liquid conversion rate in the hydroprocessing reaction zone is less than About 25% by volume. In individual instances, the present invention refers to an integrated chelating agent system used to prepare lubricant base materials. In the integrated method of producing a large amount of lubricating oil base material from a petroleum feed, the method includes: a) separating the petroleum feed into at least one light ends stream and at least one heavy ends core base --- A7 B7 V. Description of the invention (stream; b) a method for producing at least one lightweight lubricating oil base material, comprising: i) sufficient conditions to hydrolyze at least a portion of sulfur and at least a portion of nitrogen from the light ends stream under hydrocracking reaction conditions; With the middle removed, the hydrogen in the first hydrocracking reaction zone is contacted with at least one light crane component stream to generate at least one loamy light oil component. Its viscosity index is relative to the viscosity index of the light ends stream. In order to increase ii) using at least one waxy light oil component in the first dewaxing reaction zone, the reaction zone includes a layered catalyst system including a first catalyst and a second catalyst layered thereon, the first catalyst Including isomerization de-soiling catalysts; and the second catalyst is selected from the group consisting of noble metal amorphous catalysts, noble metal hydrocracking catalysts, or combinations thereof; and -ill) under conditions sufficient to produce a lightweight lubricating oil base material Hydrogenation reaction Zone contacting at least a portion of the first dewaxing reaction zone effluent; and C) a method of producing at least one heavy lubricant base material, comprising: 1) under conditions sufficient to flow at least a portion of sulfur and at least a portion of nitrogen from heavy teeth Under the middle removal, the hydrogen in the second hydrocracking reaction zone will contact the soil with one less residual stream 'to produce at least one enriched heavy oil component. Its viscosity index is relative to the viscosity index of the heavy distillate stream. In order to increase; 11) contacting at least one waxy light oil component with hydrogen in the second dewaxing reaction zone; the reaction zone includes a layered catalyst system, which includes a second catalyst and a fourth catalyst layered thereon; The three catalysts include isomerization and despironing catalysts; the fourth catalyst is selected from the following groups: precious gold (please read the precautions on the back before filling out this page) Order ---. · This paper is standard A China i χ 29Ϊ ^ ~) Α7 Β7 V. Description of the invention (It is an amorphous catalyst, a precious metal hydrocracking catalyst, or a combination thereof; and (please read the precautions on the back before filling this page) iii) It is sufficient to produce heavy lubrication Hydrogenation under oil base conditions The reaction zone is contacted with at least a portion of the effluent from the second ant-reaction zone, wherein the method for producing at least one light lubricant base and the method for producing at least one heavy lubricant base are performed simultaneously in a parallel reaction sequence. One of the advantages of this system over traditional catalyst systems is its effectiveness, as this method can be used to prepare such base oils of high quality for use in the manufacture of lubricating oils, as well as special feedstocks, which are not routinely recognized as a suitable source of such base oils. Order—. Among other factors, the present invention is based on the discovery that if the fraction of the isomerized dewaxing catalyst is replaced in the dewaxing reaction zone by a hydrogenation catalyst including a noble metal hydrogenation component, then the isomerization dewaxing oil is adjusted to a high yield. The performance of wax catalysts can be improved. Hydrotreating catalysts containing platinum / palladium alloy hydrogenation components have been found to specifically improve catalytic performance. To be clear, I have been surprised to find that adding a hydrogenation catalyst layer to an aromatic saturated dewaxing reaction zone can advance the operability of the catalytic dewaxer, reduce the effect of controlling the exothermic reaction, and improve the properties of the dewaxing oil. . It is even more surprising to include a hydrogenation catalyst layer in the dewaxing reaction zone, which reduces the stringency of the hydrocracking step before dewaxing, and affects the properties of the method to produce high-quality lubricant base materials. It is believed that at least in part because the hydrogenation catalyst effectively removes sulfur and nitrogen, opens the aromatic and cyclic structure, and increases the viscosity index of the butterfly oil before dewaxing, the loss is small or even the lubricating oil is lost. . This invention comes from the surprising development of manufacturing lubricating base oil catalyst bed _____ -8- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs- 广 I ---------- τη ι „jj, No. Patent Application No. 87111496 # 正 g ， 1 Specification Revision Page (April S9 W MW @ 7 V. Invention Description (6) Now, it can contain most different catalysts in the catalyst bed area to optimize the final and given base oil Product flow. A combination system of amorphous catalyst precious metals that provides the main benefit of increasing catalyst activity, which results in longer catalyst life, whereas the waxy portion of the dewaxing feed is catalyzed to provide a sudden increase in viscosity index and maximize yield. Attach a 5 Petroleum feed 140 Catalytic dewaxing reaction zone 10 Distillation tower 141 Catalytic dewaxing reactor 100 series is light feed 151 Hydrogenation reactor 102 Light distillate fraction 152 Oil products 110 Hydrocracking reaction zone 154 Hydrogen-rich gas stream 111 Hydrocracking reactor 156. Hydrogen-rich gas stream 120 First separation zone 160 Hydrogenation reaction zone 122 Purified hydrogen-rich gas stream 162 Effluent 124 Light weight Hydrogenated cracker 170 Separation zone 128 Light butterfly hydrogenated cracker 172 Hydrogen-containing gas stream 130 Distillation column 174 Light lubricating oil base 132 Corrosion oil portion 200 Series is heavy feed 134 Wax oil portion 202 Heavy distillation Liquid part 136 Wax oil part 274 Heavy lubricating oil base material-9- This paper uses China National Standard (CNS) A4 specification (210X297 mm) ---------- I- ^ ----- Order ------ Color (please read the precautions on the back before filling this page) No. 87111496 Patent Sheet Correction Sheet (89 ί, 4. ^ A7 B7 V. Description of the invention ( Figure 1 illustrates the flow chart of the better integration method of the present invention. Figure 2 shows the benefits of the yield of the layered dewaxing catalyst system. Figure 3 shows the benefits of the viscosity index of the layered dewaxing catalyst system. Figure 4 shows The effect of the layered dewaxing catalyst system on the catalytic activity was observed. DETAILED DESCRIPTION OF THE INVENTION The present invention refers to a layered catalyst for preparing dewaxed waxy feed in lubricating oil bases. When compared with the traditional dewaxing method using a single dewaxing catalyst In comparison, layered systems provide higher yields of high viscosity index dewaxed oils. The catalyst layer includes a noble metal hydrogenation component, and provides a hydrogenation treatment to hydroisomerize an aromatic saturated diparaffin. At least a part of the effluent of the second catalyst layer is in contact with hydrogen in the first catalyst layer containing an isomerized dewaxing catalyst. It can reduce the pour point of loamy oil by hydroisomerization and cracking, or even transform the antrum molecules in the oil into non-loamy type. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Refill this page) Feeds that can be processed in accordance with the present invention include: oils that generally have a higher pour point, which need to be reduced to a lower pour point. The applicable petroleum feed for this purpose may be selected from the following groups: #crude oil, with normal Wei point higher than about ⑽. c Petroleum Residues, Gas Oils and Vacuum Gas Oils, Distillate Residues from Atmospheric Pressure Distillation, Solvent-Asphalt Removal Petroleum Residues, Shale Oil, Recycling Oil, Petroleum-9a Approval (CNS) A4 (21GX297 mm A.7 B7 V. Description of the invention (and boiling soft paraffin, waxy petroleum feed, Naou (NAO, trade name) butterfly, and wax produced in the chemical factory method Straight-chain n-paraffins with 16 or more complete atoms are referred to herein as waxes alone or with only slightly branched paraffins. The preferred petroleum distillate has a normal boiling point range of 200. : To 700. (:, more preferably boiling at 260 ° C to 650 ° C. Suitable feeds include those heavy distillates, usually defined as heavy straight gas oils and heavy cracking cycle oils, and traditional Fluidized bed catalytic cracking feed and its parts. The cracking feed can be obtained from heating or catalytic cracking of various raw materials. The feed may be subjected to a hydrotreating and / or hydrocracking process before being supplied to the process. On the one hand, or may add more ground, the feed may be Treated in a solvent extraction process to remove aromatic compounds and sparse- and nitrogen-containing molecules. Typical feedstocks that are advantageous for processing according to the present invention often have an initial pour point above about 0. (:, more usually above about 2G) ° C. The product formed after the process usually has a pour point below about -0 ° C, and more preferably below about -10 ° C. The term "waxy petroleum feed" as used herein includes petroleum wax. The process of the invention The feed used may be a qualitative feed, # containing more than about 50% 壌, or even greater than about 90% wax. The high paraffinic feed has a pour point, usually higher than about 0 C. .More generally, the temperature is about 10 ° C, and it can also be used in the method of the present invention. The feed can contain more than about 70% paraffin stoves, and even more than about 90%. % Paraffinic carbons. Appropriate feeds can be used in the process of the present invention. R „Examples of necks include waxy distillate feeds, such as gas oils, lubricating oils, oils, and oils, such as Fischer-Tropsch method to synthesize apricots ~ odds, pour point poly-α-olefins, foot oils, synthetic wax substances, such as α-ene 杻 cloth &%, relaxation wax. Degreasing wax 10 paper thick scale into the Chinese prisoners in Sichuan (ΓΝϋ) Λ4 specification (210X297 mm --- 1--I --- 1 ---- -n τ 、-'° (Please read the notes on the back before filling this page) A7 V. Description of the invention (8)' — '—------ and slightly crystalline soil. Foot oil consists of soil and oil The prepared oil is called foot oil i. Relaxation wax can be obtained from hydrocracking lubricating oil or solvent refining lubricating oil. The addition of argon cracking is better, because this method can also reduce the nitrogen content to a low level. Solvent refining oils are derived from relaxation and deoiling can be used to reduce gas content. If necessary, a slack hydrogenation treatment can be performed to reduce its nitrogen content. The normal range of the non-relevant viscosity of the slack wax is from i40 to 200, depending on the oil content and the starting material of the wax. Relaxing waxes are therefore significantly suitable for preparing lubricating oils with a very high viscosity index, i.e. from about 120 to about 180. The layered catalyst includes a first catalyst in the reactor and a second catalyst overlying the first catalyst. The first catalyst includes an isomerized dewaxing catalyst; and a second catalyst layer on the first catalyst layer of the reactor. The second catalyst layer is selected from the group consisting of a noble metal amorphous catalyst, a noble metal hydrogenation catalyst, or a combination thereof. The catalyst layer includes a second catalyst layer having a volume ratio of about 丄 to about 70% and a first catalyst layer having a volume ratio of about 99% to about 30%. The second catalyst layer is preferably from about 5% to about 50/100% by volume, and the most preferable is from about 20 to about 30% by volume, and the remainder is the first catalyst layer. The layered catalyst that can be used in the dehydration method includes a hydrogenation catalyst selected from the group consisting of a noble metal amorphous catalyst, a noble metal hydrocracking catalyst, or a combination thereof. Useful precious metals include platinum, palladium, nails, rhodium, osmium and iridium. When the hydrotreating catalyst used in the present invention contains at least one metal, it is also possible to use a combination of two or more metals or a compound thereof, for example, a composition in which the metal contains both platinum and palladium. Most of the methods in the industry are known; DJ Platinum and surface metals or their compounds are supported on the support, for example, -11-this paper rule / ^ state towel ® (2l0X297 ^ t) ----- nnnmmn-In-- nn HI IT T 3, T (Please read the notes on the back before filling out this page) A7 B7 V. Description of the invention (9 Ion exchange, immersion, co-precipitation, etc.) Ammonia, treatment catalyst then includes the matrix material, its It is a condition for resistance to mild and other applications. The matrix material contains at least a binder, such as clay and inorganic oxides that occur in the self-effect world, to improve the crushing strength of the catalyst. A warfare matrix material, which includes a binder, It is selected from the oxides commonly used in the preparation of catalysts, including silica, alumina, magnesia, oxidized oxide, hafnium oxide. Clay can also be used. The application of the present invention is better. Subtractive preparation. The distribution of the stone and stone oxides in the oxide material can be homogeneous or uneven, but the unevenness is more preferred. The better form of the oxide matrix material contains the oxide gel adhesive. Composition, its scattered cut stones : Oxide matrix material, this form is here referred to as "non-M support". Domains can also include other refractory materials in oxide or precious stones, such as other inorganic oxides or clay particles. The conditions are This material * adversely affects the ammoniation treatment activity of the final catalyst. Other inorganic oxides that may be present in the support may include but are not emulsified, magnesium oxide, and zirconia or a combination thereof. Generally Shi Xiite _ Emulsification Ming will constitute a matrix material of at least 90% by weight and preferably up to 100% by weight but excluding oxide binders, and the matrix material: will contain from about 5 to about 70% by weight of bonding And preferably from about 20 weight percent to about 50 weight percent of the binder. Binder materials may include the following oxides: aluminum, silicon, magnesium, germanium, and zirconium. This oxide is in contrast to other oxides. Combination Yang is also useful. Oxyalumin binder is better. Amorphous catalyst of precious metal contains precious metal hydrogenation component and-amorphous (that is, non-crystalline) matrix material. Can be used in this 21 Ox 297 mm) ί, / 京 ------ (please read the notes on the back first # 异笔良 f) I ----- ·

*1T 部 Λ* 1T Section Λ

Ik 合 fl 印五、發明説明（10 A7 B7 發明之較優加氫裂解催化劑爲例如pd/Si〇2/Al 催化劑之貝金屬催化劑，其描述於如美國專利號5,3 93，4〇8號，其説明書爲所有目的計完全地於此併供參明。特優氫化處理催化劑包含鉑-免合金及和氧化物基質，其中合金中鉑對鈀的莫耳比介於約2 5 :丨至約】：2 5之間，較優介於約2 : ：1至約i : i之間，且最優鉑對鈀比爲丄：〗5。特優催化劑展現赵基催化劑之活性，且同時維持通常較低反應性鉑基催化劑之硫容忍性，如此避免需要較高之反應溫度，因其增加不受歡迎裂解反應速率且產生低穩定性的產品。此合金材料爲新催化劑種類且不同於在催化劑酸支載物上鉑及鈀金屬混合物。該‘催化劑較優依美國專利號 5，j9^,408所述内容製造，其說明書爲所有目的計完全地於此併供參照。除此完全説明書之外，送件申請共審查中案名爲杬蜆性加氫轉化催化劑及含硫潤滑進料氫化方法,，且具案件號T-5244A亦爲所有的目的完全地於此併供參照。最優氫化處理催化劑具總孔隙體積大於約〇 45立方公分/ 克、較優大於約〇_ 55立方公分/克，且具至少約} %、較優土少約j %全郅孔隙體積爲直徑大於約工〇〇〇埃之巨孔，最小巨孔體積1較優大於007立方公分/克。此處所謂術語„巨孔的‘係指催化劑具較大孔隙體積，此即至少2 %孔隙直徑大於約1000埃，最小巨孔體積量較優大於0.07立方公分/ 克。、本發明應用催化劑之孔隙尺寸分佈使用汞侵入多孔測法決疋’例如描述於美國材料試驗學會〇4284號："催化劑孔 -13 - ΙΪ n^iw 1- - - m^i I- n 11 I —M.---In I...... -I In ....... ' \ V (請先閱讀背面之注意事項再填寫本頁) 本纸依尺度適W中國丨§家標泠（ (210/ 297公漦） A7 ____ B7 五、發明説明（n) -----^-------J ! (請先閱讀背面之注意事項再填寫本頁} ，體積分佈之由紐人多孔測法"。根據此程序，催化劑在眞空450。。加熱3 0分鐘以移除蒸氣及其他揮發物。稱重的部分樣品（G345克’依總孔隙體積估計而放置在體積_ 校準刻度樣品管内。管内裝滿汞且***冠達克 (QUantaChr〇me，量子鉻，商品名）自動掃描多孔測計之壓 :化隔室内。隔室内壓力由。增加到6〇，_，磅/平方吋(大氣）。當壓力增加時，求進入樣品孔隙之内，故樣品管裡的汞體積呈現減少。表觀汞體積依所應用壓力之函數而得。表觀汞體積和應用壓力然後分別地關連到孔隙體積（V )和孔隙直徑（D)。結果報告爲以孔隙體積（單位立方公分）和累積孔隙體積（立方公分）以孔隙直徑（單位埃）之函數做圖。貝料分析給予巨孔體積百分比如依下式：巨孔體積百分比=(巨孔體積/總孔隙體積）χι〇()。放置在支載物上鉑-鈀合金的數量必須足以當作潤滑油基料氫化作用之有效催化劑。在本發明範圍裡通常用以催化氫化作用方法在支載物上合金的數量將介於由約〇〇1重量百分比到約5重量百分比的範園内，較優範圍由約〇1重量百分比到約1重量百分比。通常增加到大於約合金之〗重量百分比不顯著地改良催化劑的活性，因此爲經濟上不利的。然而。數量超過i重量百分比通常不妨害催化劑的表現0 技藝中習知許多在支載物上澱積鉑和|巴金屬或其化合物 I方法，如例如離子交換、浸入、共沉澱作用等等。其已發現當使用包含鉑和鈀兩者活性化合物之控制酸鹼値接觸 _________________-14- 本紙张尺度適冷(('NS ) Λ4^ ( 210X 297^^") A7 ---------- ----B7____ 五、發明説明（乜） '谷液時，在本發明催化劑所用支載物上澱積鉑及鋁爲特別地有利。接觸溶液較優缓衝至保持在酸鹼値由約9到約i 〇範圍内。在此酸鹼値範園外之値可用以共同地在支載物上贏積鉑和鈀，但是支载物上合金最後分配可能不像在此酸鹼値範圍内所得一樣有利。除已經描述之氫化作用成分及基質材料外，貴金屬加氫裂解催化劑可再包含活性基質之裂解成分，如—或多分子篩，包括非沸石分子篩和鋁矽酸鹽沸石，在某些條件下加入以增加催化劑之反應性及/或壽命。本方法之含沸石氫化處理催化劑通常包含約〇,丨至約2 〇重量百分比之間沸石，且較優介於約1至約1 〇重量百分比之間沸石。氫化處理催化劑之較優·滞石包括沸石Y、X及超穩γ。特優沸石具構架 SiOyAUO3比大於約1 〇，且較優大於約2 0。與沸石結合使用其他活性材料以改良轉化或催化劑選擇性亦在本發明的範圍内。然而當氫化處理催化劑之裂解活性可再由加入卣素，如氟至催化劑而增加，然催化劑實質上不含氟爲較優。經濟部中央標準局員工消費合作社印製 »n n n ! In -- 1 I . HI--- -I: -- - .....- LI 丁、T (諳先閱讀背面之注意事項再填寫本頁) 至少由脱增_反應區裡盘化處理催化劑層之流出物—部分在包含共構脱螬· ί佳化劑之催化劑層上之氫接觸。本發明氫化處理/脱徵方法之進行條件通常包括溫度落在介於由約 5 5 0°F至約850°F之範圍内，較優由約600。F至約800。F之範圍内，壓力範圍由約1 5到約3500磅/平方吋（大氣），較優由约 200到約3000磅/平方吋（大氣），且更優由約1000到約3〇〇〇磅/平方吋（大氣）。在接觸時液體每小時空間速度（LHSV) -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） A7 B7 、發明説明（Ί3 通常由約0.1至約2〇 I ί ! HI i i «4- n. I. - ! _ Τ» 、r (請先閱讀背面之注意事項再填寫本頁) 觸較優在氫存在下進ϋ優由約G.2到約1G/小時。接 w莫爾氫/每莫爾/更；^煙之比較優落在由約以到約烴之範圍之内。冬用/ 到約30個莫爾氫/每莫爾 * _ , 田在此處’液體每小時空間速度（LHSV) 表不馬油之體積/矣t砝，— 又…仙V) 時。♦脱婢之寸二時、母體積催化劑，單位爲1/小化诘二-I: I’本氫化處理方法時在氫化處理時較欲轉可二菸：。：些潤滑油基料之轉化’例如高至約25%，理:二施/ Μ用裂解轉化率爲衡量石油進料在氫化處巧換成具正L小於參考溫度u之反應產物之體積百分比，其中：Ik and fl. Imprint 5. Description of the invention (10 A7 B7 The preferred hydrocracking catalyst is a shell metal catalyst such as a pd / Si〇2 / Al catalyst, which is described in US Patent No. 5,3 93,408. No., the description of which is fully included here for all purposes and for reference. The super-hydrogenation catalyst includes a platinum-free alloy and an oxide matrix, in which the molar ratio of platinum to palladium in the alloy is between about 2 5:丨 to about]: between 2 and 5, preferably between about 2 ::: 1 to about i: i, and the optimal platinum to palladium ratio is 丄: 〖5. The special excellent catalyst exhibits the activity of Zhao Ji catalyst, and At the same time, the sulfur tolerance of the generally lower-reactivity platinum-based catalyst is maintained, thus avoiding the need for a higher reaction temperature because it increases the rate of undesired cracking reactions and produces products with low stability. This alloy material is a new catalyst type and is different It is a mixture of platinum and palladium on the acid support of the catalyst. The 'catalyst is preferably manufactured according to the content described in US Patent No. 5, j9 ^, 408, and its specification is hereby incorporated by reference for all purposes. In addition to the full specification, the application for joint review The case is named alkaline hydroconversion catalyst and sulfur-containing lubricating feed hydrogenation method, and case number T-5244A is also fully included here for all purposes and for reference. Optimal hydrogenation catalyst with total pore volume Greater than about 0,45 cubic centimeters per gram, more preferably greater than about 0 to 55 cubic centimeters per gram, and having at least about}%, less than about j% of the total soil pore volume is a giant with a diameter greater than about 0.0000 angstroms Pores, the smallest macropore volume 1 is preferably greater than 007 cubic centimeters per gram. The term "macropore" here means that the catalyst has a large pore volume, that is, at least 2% of the pore diameter is greater than about 1000 Angstroms, the minimum macropore volume The amount is more preferably greater than 0.07 cubic centimeters per gram. The pore size distribution of the catalyst used in the present invention is determined using a mercury intrusion porosity measurement method. 1---m ^ i I- n 11 I —M .--- In I ...... -I In ....... '\ V (Please read the notes on the back before filling in this (Page) This paper is suitable for China according to the scale 丨 § House standard ((210/297 gong) A7 ____ B7 V. Description of the invention (n) ----- ^ ------- J! (Please read the precautions on the back before filling out this page}, the volume distribution is determined by the Newman Porosity Test ". According to this procedure, the catalyst is emptied in the air 450. Heating for 30 minutes To remove vapors and other volatiles. Weigh a portion of the sample (G345g 'based on the total pore volume estimate and place it in a volume_calibration scale sample tube. The tube is filled with mercury and inserted into a crown dak (QUantaChromo, quantum chromium, Commodity name) Pressure of automatic scanning multimeter: chemical compartment. Pressure in the compartment. Increase to 60, _, pounds per square inch (atmospheric). When the pressure increases, it is required to enter the pores of the sample, so the mercury volume in the sample tube decreases. The apparent mercury volume is a function of the applied pressure. Apparent mercury volume and applied pressure are then related to pore volume (V) and pore diameter (D), respectively. Results are reported as a function of pore volume (in cubic centimeters) and cumulative pore volume (in cubic centimeters) as a function of pore diameter (in angstroms). The volume percentage of macropores given by shellfish analysis is as follows: Percentage of macropore volume = (megapore volume / total pore volume) x (). The amount of platinum-palladium alloy placed on the support must be sufficient as an effective catalyst for the hydrogenation of the lubricant base. Within the scope of the present invention, the amount of alloys commonly used in catalytic hydrogenation methods on a support will fall within a range from about 0.001 weight percent to about 5 weight percent, with a more preferred range from about 0.01 weight percent to about 1 weight percent. Increasing the weight percentage to more than about alloy usually does not significantly improve the activity of the catalyst and is therefore economically disadvantageous. however. An amount in excess of i% by weight usually does not hinder the performance of the catalyst. Many techniques are known in the art for depositing platinum and | barium metals or their compounds on a support, such as, for example, ion exchange, immersion, co-precipitation, and the like. It has been found that when using a controlled acid-base 値 contact containing active compounds of both platinum and palladium _________________- 14- this paper is moderately cold (('NS) Λ4 ^ (210X 297 ^^ ") A7 ----- ----- ---- B7____ V. Description of the invention (乜) 'In the valley liquid, it is particularly advantageous to deposit platinum and aluminum on the support used for the catalyst of the present invention. The contact solution is better buffered to maintain at The pH range is from about 9 to about i 0. The pH range outside the range can be used to collectively accumulate platinum and palladium on the support, but the final distribution of the alloy on the support may not be the same as in This acid-base range is equally beneficial. In addition to the hydrogenation components and matrix materials already described, the noble metal hydrocracking catalyst may further include active matrix cracking components, such as—or multi-molecular sieves, including non-zeolitic molecular sieves and aluminosilicic acid. Salt zeolite is added under certain conditions to increase the reactivity and / or life of the catalyst. The zeolite-containing hydrogenation catalyst of this method usually contains about 0.1 to about 20 weight percent zeolite, and more preferably about 1 To about 10 weight percent zeolite. Hydrogen Treatment catalysts are superior. Stagnates include zeolites Y, X, and ultra-stable γ. Extra-optimal zeolites have a framework SiOyAUO3 ratio greater than about 10, and more preferably greater than about 20. Use other active materials in combination with zeolite to improve conversion or catalyst The selectivity is also within the scope of the present invention. However, when the cracking activity of the hydrogenation catalyst can be further increased by adding halogens, such as fluorine, to the catalyst, it is better that the catalyst does not substantially contain fluorine. Consumption by employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative »nnn! In-1 I. HI --- -I:--.....- LI Ding, T (谙 Please read the precautions on the back before filling this page) At least by de-addition_ The effluent of the discontinued catalyst layer in the reaction zone-part of the hydrogen contact on the catalyst layer containing the co-structural dehydration agent. The conditions for carrying out the hydrogenation / designation method of the present invention usually include the temperature falling between In the range from about 5 50 ° F to about 850 ° F, more preferably from about 600 ° F to about 800 ° F, and the pressure range is from about 15 to about 3,500 psi (atmospheric). Preferably from about 200 to about 3000 psi (atmospheric), and more preferably from about 1000 to 300 pounds per square inch (atmospheric). Liquid hourly space velocity (LHSV) when in contact -15- This paper size applies to China National Standard (CNS) A4 specification (210x297 mm) A7 B7, invention description (Ί3 Usually from about 0.1 to about 2〇I ί! HI ii «4- n. I.-! _Τ», r (please read the precautions on the back before filling this page) Touch the best in the presence of hydrogen From about G.2 to about 1G / hour. Then Moore hydrogen / per Moore / more; the comparison of smoke falls within the range from about to about hydrocarbons. For winter use / up to about 30 Mohr hydrogen / per Moore * _, Tian here ‘Liquid hourly space velocity (LHSV) represents the volume of horse oil / 矣 t weight, — again ... sen V). ♦ Detachable inch Two-hour, mother volume catalyst, unit is 1 / min. 诘 --I: I ’In the present hydrogenation method, it is more desirable to convert during hydrogenation. : The conversion of some lubricating oil base materials is, for example, as high as about 25%, and the reason is that the conversion rate of the two applications / M is a measure of the volume percentage of the reaction product of the petroleum feed in the hydrogenation place with positive L less than the reference temperature u. ,among them:

Tref=T5〇-2.5(Τ5〇-Τ3〇) 且其中Tm和丁3〇是到氫化處理反應區石油進料根據 D2887模擬蒸鶴之分別相同於5〇%及3〇%體積之正常沸點溫度。經濟·邓中夬榡準局員工消費合作枉印製異構脱蠟催化劑包含分子篩，具孔隙直徑71埃、最優6 5 埃或較少，且具至少一孔隙直徑大於或等於4 8，及具微晶尺寸不大於約0· 5微米。催化劑特徵爲其具充份酸性以在 3 70 C至少轉化50%十六烷，且展現4 〇或更大同分異構選擇性比値’此處定義做96%十六燒轉化率。催化劑再包括至少一第VIII族金屬。應用異構脱蠟催化劑的脱蠟方法描述在美國請准專利5,282,957號，其爲所有的目的計完全地於此併供參照》分子篩爲具1 0 -或1 2 -原子環多種物質且具最大橫穿孔隙直徑不大於7.1埃。可用於本發明方法之特定分子篩包括沸 16- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐）經濟部中央標準局員工消費合作社印製 A7 B7_ 五、發明説明（14 ) 石ZSM(商品名，一種滞石非均勻催化劑）·12、ZSM-21、 ZSM-22、ZSM-23、ZSM-35、ZSM-38、ZSM-48、ZSM-57、石夕卸銘石、鎮納針；弗石、石灰（L)、SSZ(商品名，一種碎酸沸石）-3 1、SSZ-32、SSZ-3 6、SSZ-41 及SUZ(商品名，一種單矽酸沸石）-4及其他鋁难酸鹽基分子篩材料，例如： SAPO( 商品名，一種矽鋁磷酸鹽， silicoaluminophosphates)-l 1 、SAP0-31 、SAP0-41 、 MAPO(商品名，一種鎂鋁磷酸鹽，magnesium aluminophosphate) -11及MAP0-31。該分子_描述於下列各文獻：每一於此併供參照：美國專利號：3,702,886 ; 3,709,979 ； 3,832,449 ； 3,950,496 ; 3,972,983 ： 4,076,842 ; 4,016,245 ； 4,046,859 ； 4,234,231 ； 4,440,871 ： 5,053,373 ： 5,106,8 01 ;及5,591，421和美國於1996年1 2月3 1日送件申請之暫時專利申請序號60/034,252。雖然ZSM-5不符合所述的異構脱蠟催化劑孔隙大小限度，具微晶尺寸小於約〇. 5Tref = T50-2.5 (T50-T3〇) and Tm and D30 are the petroleum feed to the hydrogenation reaction zone. According to D2887, the simulated steaming crane is the same as the normal boiling point temperature of 50% and 30% by volume. . Economic · Deng Zhongxian Bureau of Consumer Consumption Co-operation, Printed Heterogeneous Dewaxing Catalysts contain molecular sieves with a pore diameter of 71 angstroms, optimal 6 5 angstroms or less, and at least one pore diameter greater than or equal to 4 8 The crystal size is not greater than about 0.5 microns. The catalyst is characterized by being sufficiently acidic to convert at least 50% of hexadecane at 3 70 C, and exhibiting an isomeric selectivity ratio of 40 or greater 値 'is defined here as a 96% hexadecane conversion. The catalyst further includes at least one Group VIII metal. A dewaxing method using an isomerized dewaxing catalyst is described in US Patent No. 5,282,957, which is hereby incorporated by reference for all purposes. The molecular sieve is a 10- or 1- 2 The transverse pore diameter is not greater than 7.1 Angstroms. Specific molecular sieves that can be used in the method of the present invention include boiling 16- This paper size applies Chinese National Standard (CNS) A4 specifications (210 × 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of the invention (14) ZSM (trade name, a heterogeneous catalyst for stagnant rock) · 12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, Shixi unloading stone, town Nano needles; fusistone, lime (L), SSZ (trade name, a fragmented zeolite) -3 1, SSZ-32, SSZ-3 6, SSZ-41, and SUZ (trade name, a monosilicate zeolite)- 4 and other aluminophosphate-based molecular sieve materials, such as: SAPO (trade name, a silicoaluminophosphates) -l 1, SAP0-31, SAP0-41, MAPO (trade name, a magnesium aluminophosphate, magnesium aluminophosphate) -11 and MAP0-31. This molecule is described in the following documents: each hereby incorporated by reference: U.S. Patent Nos .: 3,702,886; 3,709,979; 3,832,449; 3,950,496; 3,972,983: 4,076,842; 4,016,245; 4,046,859; 4,234,231; 4,440,871: 5,053,373: 5,106,8 01; No. 421 and the provisional patent application number 60 / 034,252 filed by the United States on December 31, 1996. Although ZSM-5 does not meet the pore size limit of the heterogeneous dewaxing catalyst, the crystallite size is less than about 0.5

I 微米之ZSM-5已發現爲適合當做本脱壤方法之加氫異構化催化劑。本發明之分子篩最佳化以讓最初形成之分枝系在裂解發生以前逃離催化劑孔隙系統。此由使用小微晶尺寸之分子篩及/由修正分子篩裡酸性部位之數目、位置及/或強度而得。分子篩酸性部位的數目越大，微晶大小必須越小以由同分異構化提供最少裂解之最佳化脱蠟。具很少及/或弱酸性部位之分子篩可能有較大微晶尺寸，而當分子篩具許多及/或較強酸位置時，其微晶尺寸比較小。 __ -17- 本&張尺度適用中國國家標準（〇奶）八4規格（210乂 297公釐) " '~~ —^^1 - s I «1--- —-—-I (. .....I nn - - In 5 、vd (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（15 -------—- — Ν.裝！ (請先閲讀背面之注意事項再填寫本頁) 孔隙方向裡微晶之長度爲極重要之尺寸。X -光緩射（以下簡稱XRD)可用線幅寬變測量來量測微晶長度。本發明較優微晶尺寸在許多條件下沿著孔隙方向（” c -轴"）爲 <0.5、更優£0.2、再優<0.1微米，且相對應於孔隙方向之 XRD線之XRD線寬變在這些較優微晶中觀察到。對於較小尺寸微晶而言，尤爲具微晶尺寸<0.2微米者，因爲分枝分子可更立即地在裂解以前逃離，酸度變成更不重要。當微晶尺寸爲幺0· 1微米時，此甚至更爲眞實的。對於比1到2微米更大的微晶，需要掃描電子顯微鏡（SEM)或透射電子顯微鏡（TEM)以估計微晶長度，因爲XRD線不可測地變寬。爲了要正確地使用SEM或TEM ’，分子篩催化劑必須由清楚的個別微晶组成，而非較小粒子塊集以正確地決定尺寸。因此，SEM及TEM量測之微晶長度値多少較XRD値不可使用XRD決定微晶尺寸之方法描述於克藍氏（Klug)和亞歷山大（Alexander)所著"X光繞射程序M威利（Wiley)出版社，1 9 5 4年，其於此併供參照。因此：經濟.邓中央標準局員工消費合作社印製 D=(K·λ)/(β*cos0) J 其中： D =微晶尺寸，埃。常數，約等於〜1 λ=波長，埃。 β =改正弧度之一半寬展 Θ =繞射角。 -18- 表紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 " __________B7 五、發明説明（π ) (請先閲讀背面之注意事項再填寫本頁) =微^約〇」微米長度⑼孔隙方向），減少酸性部位 2(例如以鹼金屬或鹼土金屬陽離子交換氫陽離子）可化、奪摆Μ :構選擇某—範圍。較小微晶之同分異構寸兆車又不依賴敗性，因爲分枝產品可較立即地在裂解 ^小在^同分兴構化方法時滴定（由加入鹼如氨氣（ΝΗ3)) V在操作時的酸度可增加小範圍之同分異構化選擇性。四本發明最優催化劑爲丨〇 _原子環多樣物（定義孔隙開口之 %中1 0個氧原子），其具分子篩之孔隙開口尺寸y 1埃、軚優S6.5埃。此催化劑包括ZSM_21、ZSM_22、、 ZSM-35、ZSM_38、ZSM_48、ZSM_57、脱_32、鎂鈉針滞石、5ΑΡ〇-ΐΗσΜΑΡ〇_η a其他有用分子篩包括SAp〇_3i、 SAPO-41、MAP0-31和SSZ-25，其精確的結構爲不已知的，但是其吸附特性及催化性質爲使其滿足用於本發明方法催化劑的孔隙尺寸需求。亦可用做催化劑爲i 2 _原子環沸石分子篩例如石灰（L)沸石和ZSM_12，其具不成形（非圓形）孔隙’使其滿足橫跨尺寸不大於7·〗埃之需求。經濟部中央標準局員工消費合作社印製本異構税場催化劑描述於例如美國請准專利5 282 號。其全揭示説明爲所有的目的於此併供參照。本發明使用選定酸度、選定孔隙直徑及選定微晶尺寸（對應於選定擇孔隙長度）之催化劑。如此選擇爲確保充份酸度以催化同分異構化’且使產品足夠快速地逃離孔隙系統而使裂解減至最低。孔隙直徑需求已在前述。在酸度和分子篩微晶尺寸間需有關係以提供最佳化高黏度指數油類與高的產率，其 -19- 本紙張尺度適用中國國家揉準（CNS ) A4規格（210x297公釐）經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（17 ) 由進行兴構化正十六烷進行標準同分異構化選擇性測試定義之。測試條件包括1200磅/平方吋（大氣）的壓力、160毫升/分鐘（在1大氣壓及25X：)之氫流、i毫升/小時之進料速率、及使用0.5克催化劑載入3呎長3/16吋内徑寬之不銹鋼反應器管（催化劑位於管之中心且延伸約丨至2吋長）而催化劑上游裝載鋁氧粉以預熱進料。催化劑若其合格當作本發明之催化劑，當以此方式測試時，在37〇r或更低之溫度必須至少轉換50%十六烷且在355°C以下溫度時較優轉換96% 或更多十六烷。同時當催化劑在導致96%十六烷轉化率條件下操作時’由溫度昇高所得同分異構化選擇性，其意謂產生異構化十六烷相對於裂解產物之選擇性一定爲4 〇或更大、更優爲50或更大。同分異構化選擇性，基於96%正十六烷（n C !6)轉化爲由下式定義之比率：產品中分枝Ci6重量％ --——_________XI 00 產品中分枝Cm重量％ +產品中〇13重量％此保證酸性邵位數目足以提供所需同分異構化活性但是低至足以將裂解減到最少。太少位置導致不夠催化劑活性。使用太多位置較大微晶，裂解掌握超過同分異構化。増加给定催化劑（具固定的Si〇2/Al 2〇3比率）之微晶尺寸可增加在每個孔隙中酸（舉例來説：鋁）的數目。在某微晶尺寸範圍之上裂解而非同分異構化支配反應。分子篩微晶可合適地固著至基質或多孔的基質。術語"基質"和"多孔基質"包括無機的組合物，其微晶可併合、擴教、或另一方面緊密摻混。較優基質在烴裂解方面爲非催 -20- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -------^裝-------訂 ί (請先閱讀背面之注意事項再填寫本頁) 五、發明説明（18 A7 B7 經濟部中央標準局員工消費合作社印製化活性’ &即其實質上不含酸性部位。某有的或其可由機械或化學方法造成。滿音二：質物：：固機氧化物。較優無機氧化物包括氧…：：砍自然發生或照例處理過黏土：例如膨潤土、高嶺土、难泡石、鎂鋁海泡石和多水高嶺土。、用無機氧化物基質組成微晶可由任何適#已知方成’其中微晶緊密摻混氧化物，而後者爲水合物態（例如如含水鹽、水凝膠、濕凝膠狀沈澱、或乾燥態、或其组物）。万便方法爲使用鹽類水溶液或鹽類混合物（例如矽鈉及鋁）來製備含水合單一或複數之氧化物凝膠或共膠。其氧化銨碳酸鹽（或相似鹼類）爲^至溶液中量爲足以沈澱水合物形式之氧化物。然後，沖洗沈澱以除去大多數任何办性鹽類，且使其徹底地與微晶摻混。水或调滑劑可加量爲足以輔助混合物之成形（如被擠製）。車父優異構脱壤催化劑包含中孔尺寸分子篩，其選自 SSZ-32、ZSM-23、SAPO-ll、SAP0-31 及SAP0-41或其混物。比較明確地，如貴金屬矽石氧化鋁之非晶態氫化處催化劑層放置於如美國專利號5,053，3 73所述如SSZ-32之π 構脱蠟催化劑及美國5，393，408之催化劑的頂端上面。其説明書爲所有的目的完全地於此併供參照。另一方面，層狀系統可使用於溶劑萃取、加氫裂解、化處理/異構脱蠟方法，其中脱壤催化劑之頂層爲 Pd/Si〇2/Ai2〇3之貴金屬氫化處理催化劑，其下面爲SSZ 3 2。本發明重要利益爲其橫過脱蠟催化劑系統之氫化處合酸氫水入合理異氫如理 I -- 1 m - - - 1— - - If, ID I Hi. In Hi (請先閱讀背面之注意事項再填寫本頁) -21 - 本紙張尺度適用中國國家標準（CNS ) A4規格（21 〇 X 297公t ) A7 _____B7 五、發明説明（19 ) 層本質上沒有產率損失。然而，芳族飽和化之額外黏度栺數升級發生上部氫化處理層，造成戲劇性較高產率高指數潤滑料及/或較高異構脱蠟催化劑活性和比較長的昱= 脱纖催化劑壽命。的確本發明一令人驚訏結果爲當維持择加最後黏度指數產品時，溶劑萃取之嚴格性可降低而導致較尚產率。此相反於傳统技藝，其需要增加萃取嚴格性，且如此減少產率以増加黏度指數。雖然層狀系統將與如 ZSM-5之催化脱蠟劑作用，當脱蠟催化劑與原始貴金屬矽石氧化銘催化劑層時，SSZ-32之使用爲特優。ZSM_5催化劑説明於美國專利號3,702,886及美國專利號3,700,585 ,其説明書爲所有的目的計，完全地於此併供參照。此催化劑層狀系統可使用在複合加氫裂解/氫化處理/異構脱蠟之程序及其組合，以擴充有用範圍之主要催化劑，如SSZ32、ZSM5及其類似物。經濟，那中央標準局員工消費合作社印製 n. I I In - I -- 1 - - · --1 '[4匕----I .............—- 丁萍、νβ (請先閲讀背面之注意事項再填寫本頁) 脱蠟反應條件可能是相同或不同於脱蠟反應區裡氫化處理之反應條件。典論如何，本發明的同分異構化/脱樣方法進行之條件通常包括溫度介於由約2〇〇°C到約475 °C之範圍内且壓力由約1 5到約4000磅/平方吋（大氣）之範圍内。更優壓力爲由約100到約3000磅/平方吋（大氣）。液態每小時空間速度在接觸時通常由約〇. 1到約2 〇/小時，更優由約0.2到約1 0 /小時。接觸較優在氫存在下進行。氫對烴之比率較優落在由約1.0到約50個莫爾氫氣/每莫爾烴之範圍内、更優由約1 0到約3 0個莫爾氫氣/每莫爾烴。脱蠟方法的產品爲高品質油，其適供潤滑油基料。較優 _ -22- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）經濟部中央標準局員工消费合作社印製 A7 —-----—_ _ B7 _ 五、發明説明（2〇 ) 油產TO爲具低傾點油類，其具有傾點小於約1 〇。匚，更優少於約0 °c。最優石油產品爲第π旄或第ΠΙ族油類，依美國石油組織出版物1509 :引擎油許可及認證系統"附錄£_美國石油組織基油可互換性指導方針：汽車馬達油及柴油引擎油類"。第Π族基料包含大於或等於9 〇百分比飽和物及少於或等於0.03百分比硫且具黏度指數大於或等於8〇且少於120。第III族基料包含大於或等於9〇百分比之飽和物且少於或等於0,03百分比硫且具黏度指數大於或等於12〇。測試族群種類性質的方法包括：飽和物-美國材料試驗學會 0-2007黏度指數-美國材料試驗學會D2270硫-美國材料試驗學會D-2622、美國材料試驗學會D-4294、美國材料試驗學會D-4927、及美國材料試驗學會D-3120其中之一。成品潤滑油的黏度，當在1 〇〇°C下測量的時候，通常大於2厘史托克（cSt)。在本發明方法中，蠟質加氫裂解物在脱蠟反應區裡的氫化處理催化劑層上之氫。流出物，或至少其部分，接觸包含在脱蠟反應區中之異構脱蠟催化劑層之上的氫。因此： (a) 由氫化處理催化劑層之全部流出物狀包括正常液能加氫處理過潤滑油及含氫正常氣體流。在實施本方法之一實例中’氫化處理催化劑層之全邵流出物裝载至脱蠟催化劑層。脱壤全部流出物顯示在單一反應器中具氨化處理及脱蠟催化劑層，或在分開反應器中連續層且無液體處理介於其中。 (b) 在另一實例中，加氫處理過潤滑油裴載至催化脱蠟器 -23- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） - - - ml tn i d^i nn t.\ . n n m Hr— 1J T 口 (請先閱讀背面之注意事項再填寫本頁) kl B7 經濟部中央標準局員工消費合作社印製五、發明説明（21 ) 中。聪壤所有加氫處理過油顯示上述⑷或分離氣體，可能在傳送液體、純化氣體及額外新鮮氫氣（此即補充）至脱蠟催化劑層之前純化之。 (C)在又另一貫例中，至少加氳處理過潤滑油的一部分裝載至脱蠟催化劑層上。脱蠟一部分加氳處理過石油顯示上述（b)或使用加氫處理器當做第二階段加氫裂解器，而在第二階段充份轉化而使液態產品分餾以移除裂解產物且氣體純化以移除額外硫化氫、氨、及可能輕烴氣體。在所需潤滑範園裡滞騰之加氫處理過產品的部份爲然後混合以純化氫且予以脱蠟。在本方法中，將氫化處理催化劑層全部流出物裝載至脱蠟催化劑層爲較優。現參照圖1舉例説明之較優實例，產生潤滑油基料之層狀脱蠟催化劑系統包含在整合系統中。整合系統包括分別反應操作程序之同時處理至少二個餾出液組份。大體上言，這些組份被正常沸點區別。在整合系統中，石油進料5由正常彿點分開成多數組份，其二顯示在圖1。在多數館出液組份中，至少一輕（即較低沸點）餾出液部份102及一重 (即較尚沸點）館出液部份202爲同時地在分開的反應序列中一連串的反應步驟中反應以產生至少一輕質潤滑油基料174 和至少一重質潤滑油基料274。當只有單一蒸餾塔1〇顯示時，一序列蒸餾方法，包括一或多急驟蒸餾〇)、大氣壓蒸鶴及在部分眞空下蒸餾可能應用以製造所需要之分離。輕餾份流的典型中間-沸點爲在由600T到900下之範圍，其中間-沸點爲在該溫度時，流的50%體積在標準的壓力下彿 -24- 本紙張尺度適用中國國家標準（CNS〉A4規格（210X29?公釐） —： -— 裝— (請先閲讀背面之注意事項再填寫本頁) 、-» 經濟部中央標準局員工消費合作社印製五、發明説明（22 騰。重餘份流的典型中間-沸點爲在由700下到1000T之範圍。备餘份流及重餾份流之硫含量可高至5 %重量或更高，且氮含量可能高至2 %重量比或更高。在其後描述中，首先將會參照甩來製備輕質潤滑油基料 1 74之反應序列。輕餾份流1 〇2在加氫裂解反應區u 〇裡與氫接觸’其條件是足以產生輕蠟質氫化裂解物128，其具黏度和數與輕餾份102相較爲增加。加氫裂解催化劑也將實質部分有機氮及有機硫化合物從質進料中移除。這些除去異原子化合物反應爲重要的，因有機氮及較少量有機硫化合物會爲害下游潤滑油基料處理’如脱樣和加氫完成。異原子移除反應之產品，如氨和硫化氫爲顯著地較不爲害到下游方法。此外，氨和硫化氫 σ ffc有效地和除在第一分離區^2〇中生產之氫化裂解物流 122 ’其具氮和硫含量典型地少於2 5百萬分之—，通常少於1 〇百萬分之一，而時常觀察到低至i百萬分之_或更少之水準。在加氫裂解反應區1 1 〇裡之第一加氫裂解催化劑至少包含一氫化作用成分及視需要裂解成分在氧化物支载物上。氫化作用成分可能至少是一貴金屬及/或至少—非貴金屬。; C的貝金屬包括銷、把和其他舶族成員，例如叙和旬。合適的非貴金屬包括週期表中第VA、VIA及VIIIA族元素者較優非具金屬爲絡、鉬、鶴、銘和鎳及這些金屬混合物，例如鎳-鎢合金。非貴金屬成分可在使用之前預先硫化由在增下暴露至含硫氣體，如较化氫，以轉換金屬 25- 表紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ297公釐 (請先閲讀背面之注意事項再填寫本頁) 衮- 訂五、發明説明（23 Λ7 B7 經濟部中央標準局員工消費合作社印製 :二編i應疏化物型。氯化作用成分可以任何的適奮 Μ $ 1 i _中’如由在混合步職間由浸入或交換二二:以陽離子、陰離子或中性複合體之形式併二、’，及此型之陽離子複合物將會發現便利地在滞操^又換金屬°陰離子複合物，例如庚_鹽或間鎢酸於浸潰金屬進人催化劑内。—或多活性氮化 :用成刀來源亦可與在催化劑製備時候之彿石-铭基 =才料的活性來源混合。氫化作用成分之活性來源包括：口=何物質’其具型式爲不爲害到催化劑且其將產生在 =時所需氫化作用成分，包括任何催化劑的㈣、燃燒 =減少錢。可用作氫化作用成分典型鹽類來源包括硝酸敦、乙1¾醋、硫酸醋、氣化物。、氫化作用成分之數量可由約Q_約45%重量之範圍，且 ¥由叻0.1到約_35重-里％〇精確的數量當然將會因成分的性質而改變，少高活性貴金屬，特別是銷，比較不活性 <卑金屬更需要。在本發明中所謂術語"貴金屬包括一或多対m、銀或銷。術語所謂,,卑金屬，，包括一或多弟vB，VIB及谓族金屬，包括如m鎢、鐵、鉛及鎳。通常使用卑金屬之混合物，如第域金屬錄或叙混合以第VIB族金屬鶴或细，且卑金屬通常硫化或在催化劑裝至流時或之前在催化劑裡預硫化。本方法較優催化劑包含由約i到約15%重量比範圍、及較優由約2到約10% 重量比之至少一第VIIm卑金屬，以金屬單氧化物計算，且在由約5到約30%重量比範圍、及較優由約丨〇到約25% -26- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公楚 -------— 乂； '裝-- · (請先聞讀背面之注意事項再填寫本頁)The 1 micron ZSM-5 has been found to be a suitable hydroisomerization catalyst for this de-earthing process. The molecular sieves of the present invention are optimized to allow the initially formed branches to escape the catalyst pore system before cracking occurs. This is obtained by using a molecular sieve with a small crystallite size and / or by correcting the number, position and / or strength of the acidic sites in the molecular sieve. The larger the number of acid sites on the molecular sieve, the smaller the crystallite size must be to provide optimized dewaxing with minimal cracking by isomerization. Molecular sieves with few and / or weakly acidic sites may have larger crystallite sizes, while molecular sieves with smaller and / or stronger acidic sites may have smaller crystallite sizes. __ -17- This & Zhang scale is applicable to the Chinese National Standard (〇奶) 8 4 specifications (210 乂 297 mm) " '~~ — ^^ 1-s I «1 --- —-—- I ( ..... I nn--In 5 、 vd (Please read the notes on the back before filling this page) A7 B7 V. Description of the invention (15 -------—- — Ν. 装! ( Please read the notes on the back before filling this page.) The length of microcrystals in the pore direction is a very important dimension. X-ray retardation (hereinafter referred to as XRD) can be used to measure the length of microcrystals. This invention The optimal crystallite size in many conditions along the pore direction ("c-axis") is < 0.5, more preferably £ 0.2, even better < 0.1 micron, and corresponds to the XRD line of the pore direction XRD line Broad change is observed in these better crystallites. For smaller crystallites, especially those with crystallite size < 0.2 microns, because the branch molecules can escape more immediately before cleavage, and the acidity becomes less Important. This is even more solid when the crystallite size is 幺 0.1 micron. For crystallites larger than 1 to 2 microns, a scanning electron microscope (SEM) or transmission electron microscope is required (TEM) to estimate the crystallite length, because the XRD line becomes unpredictably wide. In order to use SEM or TEM 'correctly, the molecular sieve catalyst must consist of clear individual crystallites, rather than a set of smaller particles to correctly determine the size Therefore, the length of the crystallites measured by SEM and TEM is somewhat larger than XRD. The method of determining the crystallite size by XRD cannot be described in Klug and Alexander " X-ray diffraction program M Wei Wiley Press, 1954, which is hereby incorporated by reference. Therefore: Economy. Deng printed by the Central Standards Bureau Consumer Cooperatives D = (K · λ) / (β * cos0) J where: D = Crystallite size, Angstrom. Constant, approximately equal to ~ 1 λ = Wavelength, Angstrom. Β = One-half-width extension of the correction radian Θ = Diffraction angle. -18- Table paper dimensions apply Chinese National Standard (CNS) Α4 specifications (210 × 297 (Mm) A7 " __________B7 V. Description of the invention (π) (Please read the notes on the back before filling this page) = micro ^ about 0 ″ micron length ⑼ direction of the pores), reduce acidic parts 2 (for example, with alkali metals or Alkaline earth metal cation exchange hydrogen cation) can be converted, Pendulum M: select a certain range of structures. The isomers of smaller crystallites are not dependent on failure, because branched products can be titrated more quickly when cracking ^ smaller in ^ isomorphic structure method ( By adding a base such as ammonia gas (ΝΗ3)) V, the acidity during operation can increase the selectivity of isomerization in a small range. IV. The optimal catalyst of the present invention is a variety of atomic rings (defined in% of pore opening). 10 oxygen atoms), the pore opening size of the molecular sieve is y 1 angstrom, and the excellent S6.5 angstrom. This catalyst includes ZSM_21, ZSM_22, ZSM-35, ZSM_38, ZSM_48, ZSM_57, de_32, magnesium sodium pinite, 5ΑΡ〇-ΐΗσΜΑΡ〇_η a Other useful molecular sieves include SAp〇_3i, SAPO-41, MAPO -31 and SSZ-25, their precise structures are unknown, but their adsorption and catalytic properties are such that they meet the pore size requirements of the catalysts used in the method of the present invention. It can also be used as a catalyst for i 2 _ atomic ring zeolite molecular sieves such as lime (L) zeolite and ZSM_12, which have non-formed (non-circular) pores ′ to meet the requirements of a cross dimension of no more than 7 · Angstrom. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs This heterogeneous tax field catalyst is described in, for example, US Patent No. 5,282. Its full disclosure is hereby incorporated by reference for all purposes. The present invention uses a catalyst having a selected acidity, a selected pore diameter, and a selected crystallite size (corresponding to a selected selected pore length). This was chosen to ensure sufficient acidity to catalyze isomerization 'and to allow the product to escape the pore system quickly enough to minimize cracking. The pore diameter requirements are already mentioned. There must be a relationship between acidity and the size of the crystallites of the molecular sieve to provide optimized oils with high viscosity index and high yield. The paper size is -19-. This paper applies to China National Standard (CNS) A4 (210x297 mm). Economic Printed by the Consumer Standards Cooperative of the Ministry of Standards, Ministry of Standards, A7 and B7. 5. Description of the invention (17) It is defined by the standard isomerization selectivity test conducted with the structured n-hexadecane. Test conditions include a pressure of 1200 psi (atmospheric), a hydrogen flow of 160 ml / min (at 1 atmosphere and 25X :), a feed rate of i ml / hour, and a loading of 3 feet long using 0.5 g of catalyst. / 16 inch wide diameter stainless steel reactor tube (the catalyst is located in the center of the tube and extends about 丨 to 2 inches long) and the catalyst is loaded with aluminum oxide powder upstream to preheat the feed. If the catalyst is qualified as the catalyst of the present invention, when tested in this way, it must convert at least 50% of hexadecane at a temperature of 37 ° C or lower and preferably convert 96% or more at a temperature below 355 ° C. Polyhexadecane. At the same time, when the catalyst is operated under conditions that lead to 96% hexadecane conversion, the isomerization selectivity obtained by increasing the temperature means that the selectivity to produce isomerized hexadecane relative to the cracked product must be 4 〇 or more, more preferably 50 or more. Isomerization selectivity, based on the conversion of 96% n-hexadecane (n C! 6) to the ratio defined by the formula: Branch Ci6% by weight in the product --——_________ XI 00% Cm by weight in the product + 13% by weight in the product This guarantees that the number of acidic sites is sufficient to provide the desired isomerization activity but low enough to minimize cleavage. Too few locations result in insufficient catalyst activity. With too many large crystallites in place, the cleavage mastery exceeds isomerization. Adding the crystallite size of a given catalyst (with a fixed SiO2 / Al203 ratio) increases the number of acids (for example: aluminum) in each pore. Cleavage over a certain crystallite size range rather than isomerization dominates the reaction. The molecular sieve crystallites may be suitably fixed to a matrix or a porous matrix. The terms " matrix " and " porous matrix " include inorganic compositions whose microcrystals can be merged, expanded, or otherwise intimately blended. The preferred substrate is non-catalyzed in terms of hydrocarbon cracking. -20- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Read the notes on the back before filling this page.) 5. Description of the invention (18 A7 B7 Printed Activity of Employees 'Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs' & that is, it does not contain acidic parts. Or by chemical methods. Full sound 2: Quality :: solid organic oxides. Preferred inorganic oxides include oxygen ... :: Chopping naturally occurring or conventionally treated clays: such as bentonite, kaolin, refractory stone, magnesia and sepiolite, and Multi-water kaolin. Microcrystals composed of an inorganic oxide matrix can be made of any suitable compound, in which the microcrystals are intimately mixed with the oxide, and the latter is in a hydrated state (for example, such as hydrous salts, hydrogels, wet gels). Precipitation, or dry state, or a combination thereof). A convenient method is to use a salt solution or a salt mixture (such as sodium silicon and aluminum) to prepare a single or multiple hydrated oxide gel or cogel. Its oxidation Ammonium carbonate (or similar bases) ^ To the solution is sufficient to precipitate the oxide in the form of a hydrate. Then, the precipitate is washed to remove most of any organic salts and thoroughly mixed with the microcrystals. Water or slip agent can be added in an amount sufficient The auxiliary mixture is formed (such as extruded). The vehicle carrier excellent structure de-soiling catalyst includes a mesoporous molecular sieve, which is selected from SSZ-32, ZSM-23, SAPO-ll, SAP0-31, and SAP0-41 or a mixture thereof. More specifically, the catalyst layer of the amorphous hydrogenation site, such as the noble metal silica alumina, is placed on a π-structure dewaxing catalyst such as SSZ-32 as described in US Patent No. 5,053, 3 73 and a catalyst as described in US 5,393,408. The top is above. Its description is hereby incorporated by reference for all purposes. On the other hand, the layered system can be used for solvent extraction, hydrocracking, chemical treatment / isomerization dewaxing methods, among which The top layer is a noble metal hydrotreating catalyst of Pd / Si〇2 / Ai2 03, and the bottom is SSZ 32. The important benefit of the present invention is that it crosses the dewaxing catalyst system in the hydrogenation treatment of acid hydrogen water into a reasonable isohydrogen as the reason I -1 m---1---If, ID I Hi . In Hi (Please read the notes on the back before filling this page) -21-This paper size is applicable to China National Standard (CNS) A4 (21 〇X 297g t) A7 _____B7 V. Essence of Invention (19) Layer Essence There is no yield loss. However, the upgrade of the additional viscosity of the aromatic saturation occurs in the upper hydrotreating layer, which results in a dramatic higher yield of high index lubricants and / or higher isomerization dewaxing catalyst activity and a longer Yu = desulfurization. Fiber catalyst life. Indeed, a surprising result of the present invention is that the stringency of solvent extraction can be reduced while maintaining the final viscosity index product, leading to higher yields. This is in contrast to traditional techniques, which require increased extraction stringency, and thus reduce the yield to increase the viscosity index. Although the layered system will work with catalytic dewaxing agents such as ZSM-5, the use of SSZ-32 is particularly advantageous when the dewaxing catalyst and the original precious metal silica oxide catalyst layer are used. ZSM_5 catalyst is described in U.S. Patent No. 3,702,886 and U.S. Patent No. 3,700,585, the description of which is for all purposes, and is fully incorporated herein by reference. This catalyst layered system can be used in the complex hydrocracking / hydrotreating / isotactic dewaxing process and its combination to expand the useful range of major catalysts, such as SSZ32, ZSM5, and the like. Economy, printed by the Consumer Standards Cooperative of the Central Bureau of Standards n. II In-I-1--· --1 '[4dagger ---- I .............-- Ding Ping, νβ (Please read the notes on the back before filling this page) The dewaxing reaction conditions may be the same or different from the hydrogenation reaction conditions in the dewaxing reaction zone. In general terms, the conditions for carrying out the isomerization / sampling method of the present invention generally include a temperature in the range of from about 200 ° C to about 475 ° C and a pressure of from about 15 to about 4,000 psi. Within square inches (atmospheric). A more preferred pressure is from about 100 to about 3000 psi (atmospheric). The liquid hourly space velocity during contact is usually from about 0.1 to about 20 / hour, more preferably from about 0.2 to about 10 / hour. The contacting is preferably performed in the presence of hydrogen. The hydrogen-to-hydrocarbon ratio preferably falls within a range from about 1.0 to about 50 moles hydrogen per mole hydrocarbon, more preferably from about 10 to about 30 moles hydrogen per mole hydrocarbon. The product of the dewaxing method is high-quality oil, which is suitable for lubricant base materials. Better _ -22- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 —-----—_ _ B7 _ V. Description of the invention ( 2) Oil production TO is a low pour point oil with a pour point of less than about 10%. Alas, better than about 0 ° c. The best petroleum products are Group π 旄 or Group III oils, according to American Petroleum Organization Publication 1509: Engine Oil Licensing and Certification System " Appendix £ _ American Petroleum Organization Guidelines for Interchangeability of Base Oils: Automotive Motor Oils and Diesel Oil Engine oils ". The Group Π base material contains greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and has a viscosity index greater than or equal to 80 and less than 120. The Group III base material contains greater than or equal to 90 percent of saturates and less than or equal to 0.03 percent sulfur and has a viscosity index of greater than or equal to 120. Methods for testing the properties of species include: Saturates-American Society of Materials Testing 0-2007 Viscosity Index-American Society for Testing Materials D2270 Sulfur-American Society for Testing Materials D-2622, American Society for Testing Materials D-4294, American Society for Testing Materials D- 4927, and one of the American Society for Testing and Materials D-3120. The viscosity of the finished lubricant, when measured at 1000 ° C, is usually greater than 2 centimeters Stokes (cSt). In the method of the present invention, the hydrogen of the waxy hydrocrack on the hydrogenation catalyst layer in the dewaxing reaction zone. The effluent, or at least a portion thereof, is in contact with the hydrogen contained in the dewaxing catalyst layer in the dewaxing reaction zone. Therefore: (a) The total effluent from the hydrotreating catalyst layer includes normal liquid capable of being hydrotreated with lubricating oil and normal hydrogen-containing gas flow. In one example of carrying out this method, the entire effluent of the 'hydrogenation catalyst layer' is loaded onto the dewaxing catalyst layer. The entire effluent of de-soiling shows ammoniated and dewaxed catalyst layers in a single reactor, or continuous layers in separate reactors with no liquid treatment in between. (b) In another example, the hydrotreated lubricating oil was loaded into the catalytic dewaxer. 23- This paper size applies to China National Standard (CNS) A4 (210X 297 mm)---ml tn id ^ i nn t. \. nnm Hr— 1J T-port (please read the precautions on the back before filling this page) kl B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of Invention (21). All hydrotreated oils in Congyang show that the above-mentioned plutonium or separated gas may be purified before transferring the liquid, purified gas, and additional fresh hydrogen (that is, supplemented) to the dewaxing catalyst layer. (C) In still another embodiment, at least a part of the treated lubricating oil is loaded on the dewaxing catalyst layer. Dewaxing a part of the treated petroleum shows that (b) above or using a hydrotreating unit as the second stage hydrocracker, and in the second stage is fully converted to fractionate the liquid product to remove the cracked products and the gas is purified to Removes additional hydrogen sulfide, ammonia, and possibly light hydrocarbon gases. The portion of the hydrotreated product that stagnates in the desired lubrication range is then mixed to purify the hydrogen and dewax. In this method, it is preferable to load the entire effluent of the hydrogenation catalyst layer to the dewaxing catalyst layer. Referring now to the preferred example illustrated in FIG. 1, a layered dewaxing catalyst system for producing a lubricant base is included in the integrated system. The integrated system includes simultaneous processing of at least two distillate components while operating separately. In general, these components are distinguished by normal boiling points. In the integrated system, the petroleum feed 5 is divided into multiple arrays by the normal buddha. The second is shown in Figure 1. In most of the components of the liquid outlet, at least one light (ie lower boiling point) distillate portion 102 and one heavy (ie, lower boiling point) distillate portion 202 are simultaneously a series of reactions in separate reaction sequences. The reaction in the step produces at least one light lubricant base 174 and at least one heavy lubricant base 274. When only a single distillation column 10 is shown, a sequential distillation process, including one or more flash distillations, atmospheric pressure cranes, and distillation under partial airspace may be applied to produce the required separation. The typical middle-boiling point of a light ends stream is in the range of from 600T to 900, and the middle-boiling point is at this temperature, 50% of the volume of the stream is at a standard pressure. Buddha-24- This paper size applies to Chinese national standards (CNS> A4 specification (210X29? Mm) — — — — Loading — (Please read the notes on the back before filling out this page),-»Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (22 Teng The typical middle-boiling point of the heavy residue stream is in the range from 700 to 1000 T. The sulfur content of the spare and heavy distillate streams can be as high as 5% by weight or higher, and the nitrogen content can be as high as 2%. Weight ratio or higher. In the description that follows, the reaction sequence for preparing light lubricating oil base 1 74 will first be referred to. The light ends stream 102 is contacted with hydrogen in the hydrocracking reaction zone u 0 'The conditions are sufficient to produce a light waxy hydrogenated pyrolysate 128, which has a viscosity and a number that are increased compared to the light fraction 102. The hydrocracking catalyst also removes a substantial portion of organic nitrogen and organic sulfur compounds from the mass feed. These reactions to remove heteroatomic compounds are important because of organic And smaller amounts of organic sulfur compounds will harm downstream lube base material processing such as de-sampling and hydrogenation. The products of the heteroatom removal reaction, such as ammonia and hydrogen sulfide, are significantly less harmful to downstream processes. In addition Ammonia and hydrogen sulfide σffc are effective in addition to the hydrocracking stream 122 'produced in the first separation zone ^ 20, which typically has a nitrogen and sulfur content of less than 2.5 parts per million—and typically less than 10%. 1 part per million, and levels as low as i parts per million or less are often observed. The first hydrocracking catalyst in the hydrocracking reaction zone 110 includes at least one hydrogenation component and if necessary The cleavage component is on the oxide support. The hydrogenation component may be at least one precious metal and / or at least-non-precious metal .; C shell metals include pins, handles, and other members of the ship family, such as Syria and China. Suitable non-precious metals Including those from Group VA, VIA and VIIIA in the Periodic Table, the preferred non-metals are metal, molybdenum, crane, Ming and nickel and mixtures of these metals, such as nickel-tungsten alloys. Non-noble metal components can be vulcanized in advance before use. Increased exposure to sulfur For the conversion of metal, such as hydrogen, the standard of 25-sheet paper is converted to Chinese National Standard (CNS) A4 specifications (21 × 297 mm (please read the precautions on the back before filling this page). 衮-Order 5. Description of the invention (23 Λ7 B7 Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: the second part should be phosphate type. The chlorination component can be any suitable amount. $ 1 i _ 中' such as by immersion or exchange in the mixing step. 22: In the form of cationic, anionic or neutral complexes, the two, ', and this type of cationic complexes will be found conveniently in the stagnation process and then change the metal ° anionic complexes, such as heptyl salts or metatungsten The acid immerses the metal into the catalyst. —Or multi-active nitridation: The knife source can also be mixed with the fossil-mingji = active source that is expected when the catalyst is prepared. The active sources of hydrogenation ingredients include: Mouth = what substance 'has a type that does not harm the catalyst and it will produce the required hydrogenation ingredients, including any catalyst's tritium, combustion = reduce money. Typical salt sources that can be used as hydrogenation ingredients include nitric acid, ethyl acetate, sulfuric acid vinegar, and vapors. The amount of hydrogenation ingredients can range from about Q_about 45% by weight, and ¥ from 0.1 to about _35 weight-mile%. The exact amount will of course change due to the nature of the ingredients, less highly active precious metals, especially It is a pin, more inactive < base metal is more needed. The term "precious metal" as used in the present invention includes one or more 対 m, silver or pins. The term so-called, base metals, includes one or more brothers vB, VIB, and group metals, including, for example, tungsten, iron, lead, and nickel. Mixtures of base metals are commonly used, such as Group VI metal or alloys, and Group VIB metal cranes or fines, and base metals are usually vulcanized or pre-sulfided in the catalyst when or before the catalyst is charged to the stream. The preferred catalyst of this method comprises at least one VIImth base metal ranging from about i to about 15% by weight, and more preferably from about 2 to about 10% by weight, calculated as a metal single oxide, and from about 5 to About 30% weight ratio range, and better from about 丨 0 to about 25% -26- This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 Gong Chu ---- ----乂; '' --- (Please read the precautions on the back before filling this page)

,1T A7 B7 24 五、發明説明（ $比至少一第VIB族金屬，以金屬三氧化物計算。、弟一加氫裂解催化劑的裂解成分可能包括非晶態裂解成分’例如矽石氧化鋁，及/或大孔隙鋁矽酸鹽沸石之混合 :：例如：如X、Y、超穩Y沸石、去鋁酸根Y及八面沸石。备在最寬廣實例内，多種沸石適合加氫裂解方法，較優1弗石具低至中度總酸度，典型Si02/A1203的莫耳比由約τ5 到約100範圍内、更優由約10到約60範園内。雖然咸信潤 ^油產率爲不受使用低Si〇2/Al2〇3比之沸石的顯著影響，低饧値、低沸點產品傾向於在高轉化、低Si〇2/Ai办比滞石之加氫裂解期間產生。使用具較高siG2/Al2G3_石傾向於產生具衩南沸點之非潤滑油部份。爲了最佳化通常衝突之目的：低催化劑污髒比率及催化劑高黏度指數選擇性，催化浏在典揮發性物質基準上，通常包含少於約、較優少 10 /。且更優少於約8 %、且仍更優介於約2到約6 %範圍之沸石。沸石可旎組成是具多孔無機氧化物基質的材料及基質材料I混合物，例如矽石、氧化鋁、矽石_氧化鋁、氧化鈦、乳化鎂、矽石-氧化鎂、矽石_氧化锆、矽石-二氧化釭、矽石-氧化鈹、以·氧化鈇、氧錢_氧化锆、及如♦石-氧化鋁-二氧化鉦、矽石_氧化鋁_氧化鈦、矽石_氧化鋁-氧化鎂和碎石-氧化鎂·氧化锆之三元組合物。基質可能是以共膠的形式。親優支載物材料以幫助催化劑製備且改良催化劑物理性質者爲氧化銘支載物。甚至更優是具梦石氧化铭基質材料的滞石組合，具至少1%額外加添之氧化慈黏合 -27- t紙張尺度適财目g]家縣（CNS ) Α4規格(ΊΙο^^Τ n Ί—--In I I - I、 ^ n n n n n _Γ T ^ 、\-a (請先閱讀背面之注意事項再填寫本頁j 經濟部中央標準局員工消費合作社印製經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（25 ) 劑。較優加氫裂解催化劑具孔隙結構，其提高加氫裂解催化劑的績效以產生潤滑油基料，其包括的孔隙體積在由約 0.25至約0.60立方公分/克之·間範圍裡，平均孔隙直徑在约 4 0埃至約1 〇〇埃之間，且至少約百分之5的孔隙體積爲具直徑大於約200埃之孔隙，且至少約百分之1的孔隙體積爲具直徑大於1000埃之孔隙。此處所謂"平均孔隙直徑”參照至累積孔隙體積對孔隙直徑作圖-之圖上對應至催化劑的總孔隙體積之50%的點，如由汞測孔隙術或氮物理吸附測孔隙術測量之。可用於本方法之一此種加氫裂解催化劑爲描述於美國專利權5,543,035號，其説明書爲所有的目的計完全地於此併供參照。典型地加氫裂解條件包括溫度介於400下到950下的範園、壓力介於由500到3500磅/平方吋（大氣）的範圍、液體每小時空間速度介於0.1到20.0/小時的範圍、而且總氫供應 I介於由200到20,000標準立方呎氫/每桶烴質進料的範圍。應用前面的加氫裂解條件，進料轉化成氫化裂解物產品可製成至由約1 0到約80重量百分比之範園内。然而，較南的轉化率通常造成較低的選擇性和較大量輕質而非中間館出液或潤滑油沸騰範圍之產品。因此，必須在轉化和選擇性之間獲得妥協’且轉化在由約1 0到約7 0百分比之範圍中爲較優。達成所欲目的之反應條件間的平衡是技藝中平常技術的部分。當用在此處，所謂轉化爲沸點高於目標溫度之邵份進料轉換成產品沸點低於該溫度。通常目標溫度 -28 - 本紙張尺度適用巾家標準（CNS) A4規格（21Qx]97公楚） —；— (請先閱讀背面之注意事項再填寫本頁) V f^n ta n^i (til nn · ---^ 策------"訂經濟部中央標準局員工消費合作社印製 A7 -------B7 五、發明説明（2Θ ) 爲概算爲進料沸點最小時。包含加氫裂解反應區110的加氫裂解反應器ιη也可在操作時當做具至少二催化劑層之層狀催化劑系統，且本方法轉換:fe質進料流之潤滑油加氫裂解催化劑，該進料流爲早先地在第-加氫轉化催化劑層中處理。在層狀催化劑系統中，在進料與潤滑油加氫裂解催化劑接觸之前先由第一加氫轉化層進行-些裂解且由進料中移除氮和硫。較優產品離開催化劑最頂層的有機氮含量爲少於5〇〇百萬分之一、更優！/毛250百萬分之一、及仍更優少於1〇〇百萬分之一。催化劑最頂層通常將包含加氫轉化催化劑，包括第V〗族及或第VIII族氫化作用成分切石或珍石·氧化銘支載物上。氮化處理催化劑之較優氫化作用成分包括鎳、_、鎢和姑或其组合物。如Y-塑滞石之活性彿石，及較優具Si〇2/Ai2〇3 小於約10之活性γ_型沸石可包含在氫轉化催化劑中以增加活性和催化劑穩定性。在各種不同的催化劑層用的催化劑相對量對每個所用反應器系統及進料流而言爲特定的，其決定於例如：操作條件之嚴格性、進料的沸程、進料裡如氮和硫等異原子的量、及所欲潤滑油基料之性質。典型地在包括加氫轉化催化劑層及潤滑油加氫裂解催化劑層之催化劑系統中，加氫轉化催化劑對加氳裂解催化劑之體積比爲在介於約1/9 9至約99/1範圍之間、較優由約1〇/9〇至約 5 0 / 5 0之間。在加氫轉化催化劑層裡之加氫轉化反應條件可能是相同於或不同於在加氫裂解層之條件。通常，加氫轉化條件包 -29- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 1^------1---装------^訂 (請先閲讀背面之注意事項再填寫本頁) 五經濟部中央標準局員工消費合作社印製 A7 B7 '發明説明（27 括/皿度介於400 F到950T的範園、壓力介於由500到3500磅 /平方吋（大氣）的範圍、液體每小時空間速度介於〇. 1到 20.0/小時的範圍、而且總氫供應量介於由到標準互方呎氫/每桶烴質進料的範圍。在圖1實例中舉例説明，由加氫裂解反應區i〗〇流出物包括正常地氣體流，其包含氫、硫化氫、氨及低沸點烴質反應產物。液體和氣體產品在第—分離區】2〇分開以產生純化富氫氣體流122和輕質蠟質氫化裂解物流124。不顯示分離和純化方法的細節，其在技藝中爲習知。此細節包括方式由氣體流中除去硫化氫、氨和其他污染物以產生純化富氫氣體流122以適供再循環或爲其他精煉廠使用❶. 由本加氫裂解方法產生輕質蠟質氫化裂解物124將具高黏度指數、低氮含量和低硫含量。在額外處理之前，其可能在蒸餾塔13〇中蒸餾成不同沸點之二或更多組份，且每個纽份其特徵爲特定黏度、特定黏度指數及特定氮和特定硫含量。。爲此描述目的計，顯示任意的三個數目蠟質油部份132、 134和136。不顯示者是非潤滑油流，其使用在精煉廠別處’如當作燃料。通常。至少其中—組份將具黏度指數大 A为7 0和衩優大於约8 〇。然而。黏度指數可能高至如9 5 或甚至U0 ’ |被處理之進料⑥定。#決定螺質料黏度指數 I方法馬有效B寺’此處所得黏度指&値爲基於溶劑脱螺條件，此即，其爲基於已經溶劑脱蠟過之潤滑油基料上，使用技藝中廣爲人知方法至]代傾點。在圖1特定實例中， __-30- 本纸银尺度適用中國國家標準（CNS ) M規格（2ι〇χ297公 (請先閱讀背面之注意事項再填寫本頁}1T A7 B7 24 V. Description of the invention ($ than at least one Group VIB metal, calculated as metal trioxide. The cracking component of the first hydrocracking catalyst may include an amorphous cracking component such as silica alumina, And / or macroporous aluminosilicate zeolites: For example: such as X, Y, ultra-stable Y zeolite, deluminate Y and faujasite. In the widest range of examples, a variety of zeolites are suitable for hydrocracking methods, The superior 1 fusi has a low to moderate total acidity, and the molar ratio of typical Si02 / A1203 ranges from about τ5 to about 100, and more preferably from about 10 to about 60. Although the oil yield of Xianxinrun is Not significantly affected by the use of zeolites with a low Si02 / Al2O3 ratio, low-ytterbium and low-boiling products tend to be produced during the hydrocracking of high-conversion, low Si02 / Ai ratio specific sludge. Higher siG2 / Al2G3_stones tend to produce non-lubricating oil parts with a boiling point in southern Luan. For the purpose of optimizing the usual conflicts: low catalyst fouling ratio and high viscosity index selectivity of catalysts, catalyzed by typical volatile substances On the basis, usually contains less than about, preferably less than 10 /., And more preferably less than About 8%, and still more preferably in the range of about 2 to about 6%. Zeolite can be composed of a porous inorganic oxide matrix material and a mixture of matrix materials I, such as silica, alumina, silica_alumina , Titanium oxide, emulsified magnesium, silica-magnesia, silica_zirconia, silica-rhenium dioxide, silica-beryllium oxide, hafnium oxide, oxygen_zirconia, and such as silica-alumina -Ternary composition of hafnium dioxide, silica_alumina_titanium oxide, silica_alumina-magnesium oxide, and crushed stone-magnesium oxide · zirconia. The matrix may be in the form of co-adhesive. The oxide materials are supported by oxide materials to help the catalyst preparation and improve the catalyst's physical properties. Even more preferred is a stagnant stone combination with a dream stone oxide matrix material, with at least 1% additional oxidative bond -27- t Paper size suitable financial g] Jiaxian (CNS) Α4 size (规格 Ιο ^^ Τ n Ί --- In II-I, ^ nnnnn _Γ T ^, \ -a (Please read the precautions on the back before filling this page j Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (25). The better hydrocracking catalyst has a pore structure, which improves the performance of the hydrocracking catalyst to produce a lubricating oil base, which includes a pore volume ranging from about 0.25 to about 0.60 cubic centimeters / In the range of grams, the average pore diameter is between about 40 angstroms and about 100 angstroms, and at least about 5 percent of the pore volume is pores with a diameter greater than about 200 angstroms, and at least about 1 percent The pore volume is a pore with a diameter greater than 1000 angstroms. The "average pore diameter" here refers to the point where the cumulative pore volume is plotted against the pore diameter-the point corresponding to 50% of the total pore volume of the catalyst. It is measured by mercury porosimetry or nitrogen physical adsorption porosimetry. One such hydrocracking catalyst that can be used in this process is described in U.S. Patent No. 5,543,035, the description of which is hereby incorporated by reference for all purposes. Typical hydrocracking conditions include a range of temperatures ranging from 400 to 950 ° C, pressures ranging from 500 to 3500 psi (atmospheric), and liquid hourly space velocity ranging from 0.1 to 20.0 / hour Moreover, the total hydrogen supply I ranges from 200 to 20,000 standard cubic feet of hydrogen per barrel of hydrocarbonaceous feed. Using the previous hydrocracking conditions, the feed can be converted into a hydrocrack product to a range of from about 10 to about 80 weight percent. However, souther conversions often result in products with lower selectivity and larger amounts of light weight rather than intermediate effluent or lubricant boiling ranges. Therefore, a compromise must be achieved between transformation and selectivity, and transformation is better in a range from about 10 to about 70 percent. The balance between the reaction conditions to achieve the desired purpose is part of the ordinary skill in the art. When used herein, a so-called conversion to a boiling point above the target temperature is converted to a product having a boiling point below this temperature. Normal target temperature -28-This paper size applies CNS A4 (21Qx) 97 Gongchu — — — (Please read the precautions on the back before filling this page) V f ^ n ta n ^ i ( til nn · --- ^ tactics ------ " Order printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to print A7 ------- B7 V. Description of the invention (2Θ) is the approximate estimate for the boiling point of the feed The hydrocracking reactor including the hydrocracking reaction zone 110 can also be used as a layered catalyst system with at least two catalyst layers during operation, and the method is converted: a lubricating oil hydrocracking catalyst of a fe feed stream This feed stream was treated earlier in the first hydroconversion catalyst layer. In a layered catalyst system, some cracking is performed by the first hydroconversion layer before the feed is contacted with the lubricating oil hydrocracking catalyst. And the nitrogen and sulfur are removed from the feed. The organic nitrogen content of the better product leaving the top layer of the catalyst is less than 500 parts per million, better! / 250 parts per million, and still better Less than 100 parts per million. The topmost layer of the catalyst will typically contain a hydroconversion catalyst, including Group V and / or Group VIII hydrogenation components are cut on stone or precious stone and oxide support. The preferred hydrogenation components of nitriding catalysts include nickel, tungsten, tungsten, and their combinations. For example, Y-plastic Reactive stone of stagnant stone, and more active γ-type zeolite with Si〇2 / Ai203 less than about 10 may be included in the hydrogen conversion catalyst to increase the activity and catalyst stability. Used in various catalyst layers The relative amount of catalyst is specific to each reactor system and feed stream used, and is determined by, for example, the severity of the operating conditions, the boiling range of the feed, the amount of heteroatoms such as nitrogen and sulfur in the feed, And the properties of the desired lubricating oil base. Typically in a catalyst system including a hydroconversion catalyst layer and a lubricating oil hydrocracking catalyst layer, the volume ratio of the hydroconversion catalyst to the hydrocracking catalyst is between about 1 / 9 9 to about 99/1, preferably from about 10/90 to about 50/50. The conditions of the hydroconversion reaction in the hydroconversion catalyst layer may be the same or different. Under the conditions of hydrocracking. Generally, hydroconversion Packages-29- This paper size applies to Chinese National Standard (CNS) Α4 size (210X 297 mm) 1 ^ ------ 1 --- installation ------ ^ order (please read the first Note: Please fill in this page again.) A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. (Invention Note (27 including Fanyuan with a degree between 400 F and 950T, pressure between 500 and 3500 psi) (Atmospheric) range, liquid hourly space velocity ranging from 0.1 to 20.0 / hour, and total hydrogen supply range from to standard square feet of hydrogen per barrel of hydrocarbonaceous feed. In the example of Figure 1, the effluent from the hydrocracking reaction zone i0 includes a normal gas stream containing hydrogen, hydrogen sulfide, ammonia, and low-boiling hydrocarbonaceous reaction products. The liquid and gas products are separated in a 20th separation zone to produce a purified hydrogen-rich gas stream 122 and a light waxy hydrocracking stream 124. Details of the isolation and purification methods are not shown, which are well known in the art. This detail includes ways to remove hydrogen sulfide, ammonia, and other contaminants from the gas stream to produce a purified hydrogen-rich gas stream 122 suitable for recycling or for use in other refineries. 轻 Light waxy hydrocracking by this hydrocracking process The substance 124 will have a high viscosity index, a low nitrogen content and a low sulfur content. Before additional treatment, it may be distilled into two or more components with different boiling points in the distillation column 13 and each component is characterized by a specific viscosity, a specific viscosity index, and a specific nitrogen and specific sulfur content. . For the purposes of this description, any three number of waxy oil portions 132, 134, and 136 are shown. What is not shown is a non-lubricant stream, which is used elsewhere in the refinery 'as fuel. usually. At least one of them—the component will have a viscosity index large A of 70 and a good one greater than about 80. however. The viscosity index may be as high as 9 5 or even U0 ′ | determined by the feed being processed. #Determining the viscosity index of the snail material I method Ma effective B Temple 'The viscosity obtained here refers to & 値 is based on solvent de-snailing conditions, that is, it is based on the lubricating oil base material which has been dewaxed by the solvent. Known method to] generation pour point. In the specific example in Figure 1, __- 30- The silver scale of this paper applies the Chinese National Standard (CNS) M specification (2ι〇χ297) (Please read the precautions on the back before filling this page}

A7 A7 經濟部中央標準局員工消費合作社印製五、發明説明（28 ) 每個«石油組份，在包含催化脱樣反應區14Q之催化脱壇反應器141裡隔離操作中，依次個別處理。催化的脫蠟反應區140包含本發明層狀催化劑系統。包括貴金屬A化處理催化劑之第一催化劑層㈣料中移除硫和氮、打開芳族及脂族的環結構、和増加進料的黏度指數。包括本發明異構脱蠟催化劑之第二催化劑層降低加氫異構化反應後進料的傾點。層狀催化劑系統層及異構脱蠟催化劑層產生低傾點、高產率、高品質之脱蠟基油。來自脱蠟反應區140之脱蠟油產品152的傾點希望具傾點小於約5°C、較優少於約〇。(：、及更優小於約_5汜。本發明方法也可合併以傳統脫蠟方法而達成具特別需要性貝之潤滑油。例如本發明方法可用以減少潤滑油的傾點至所需程度。然後傾點之進一步降低可由使用傳統的脱蠟方法而達成。在此環境之下，跟隨本發明同分異構化方法後，潤滑油立刻可具傾點大於約15T。再者，本發明方法產生潤滑油的傾點可由加入傾點抑制劑组合物而減少。由圖1裡催化脱壤反應區142流出物包含脱壤輕油部份1 52 和富氫氣體流1 54。脱蠟輕油部份爲混合以富氫氣體流 156，且在氫化作用反應器151内包含之氫化作用反應區16〇内氫化作用催化劑接觸。在較優實例中，由脱蠟反應區之全邵流出物142，在未分離及未加入氫或富氫氣體流下，接觸在氫化作用反應區16 0，其條件爲足以產生輕質潤滑油基料174。由氫化作用反應區1 60之流出物1 62爲在分離區1 70 中分開’而回收含氫氣體流1 72以使用在精煉廠別處或處 -31 - 本紙張尺^適用中國國家標準（CNS ) Α4規格（210Χ 297公楚Ί ' ： --- 1- - I---- - I - - - —1 -- !·.. |士氏 I. II I - II I I — I ι-f— ^~~· 、τ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 ------- B'7__ 五、發明説明（29 ) 〜—~ ^潤滑油基料174爲回收使用作潤滑油基料。氫化作似化劑在製備，潤滑油基料中具改良脱蠛油儲存穩定性之活 ’=。如移除芳族化合物、含氮及含硫分予及色體至非常低 /辰度I反應，當將裂解反應產率損失減到最少時，特別地令人所欲。氫化作用步驟較優催化劑包含氧化物基質材料上的氫化作用成分。氫化作用成分至少可能是—貴金屬及/ 或至^ 一非貴金屬。合適的貴金屬包括鉑、鈀和其他鉑族的成員，例如銥和釕。合適的非貴金屬包括週期表中第 VA、VIA及VIIIA族元素者。較優非貴金屬爲鉻、鉬、鎢、鈷和鎳及這些金屬混合物，例如鎳_鎢合金。非貴金屬成刀可在使用之前預先硫化，由在增溫下暴露至含硫氣體，如硫化氫，以轉換金屬氧化物成相對應硫化物型。氣化作用成分可以任何的適當方法併合至催化劑中，如由在混合步驟期間由浸入或交換混合。氫化作用成分的數量可從約0.01到約4 5重量百分比之範圍内且通常由約〇」到約3 5 重量百分比。精確的數量當然將因成分性質而改變，較少局活性的貴金屬，特別是銷，比較不活性之卑金屬更需要。較優氫化作用催化劑包括介於〇.!重量百分比及1重量百分比之間的鉑及/或鈀在氧化鋁或矽石-氧化紹上，包含鉑-鈀合金具合金内鉑對鈀的莫耳比介於約2 5 : i至i ·· 2.5 之間、較優介於2 : 1至1 : 1之間，且最優等於約i : 1.5。最優氫化作用催化劑具總孔隙體積大於約〇 45立方公分/ 克、較優大於約0.55立方公分/克，且至少約1%、和較優至少約3 %總孔隙體積爲直徑大於約1 〇〇〇個埃的巨孔，及最 -32- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -- «» - II . (請先聞讀背面之注意事項再填寫本頁j 裝 .訂. A7 _____ B7 ~ '丨 — 五、發明説明（3〇 ) 小量的巨孔體積較優大於0.07立方公分/克。當此處所用術語"巨孔’’亦指催化劑具較大量孔隙體積，此即至少i %孔隙的直徑大於約1000埃’且最小巨孔體積較優大於〇 07立方公分/克。在圖1 ’ 一反應序列處理重質進料，其使用參照碼爲2〇〇系列，相配於上述處理輕質進料使用參照碼爲1 〇〇系列之反應序列。爲避免重複，產生重質潤滑油基料274反應序列之一詳細描述將不在此包括。當催化劑用在相對應反應區時 (例如第一加氫裂解反應區1 1 〇和第二加氫裂解反應區2丨〇等等）爲不必然一致，其落在此處所述催化劑説明書内。圖1舉例説明方法爲提供單一來源進料經在分餾器1 0至整合方法。在實務上，到第一加氫裂解反應區之餾份j 〇 2 及到第二加氫裂解反應區之餾份202可能來自不同的來源。因此，如同非限制例，102和202之一可能來自眞空氣體石油流，且另一可能來自蠟質進料，如鬆弛蠟或蠟質石油進料，以產生第III族潤滑油基料。經濟部中央標準局員工消費合作社印製 m J - I - - - -- I I - -_I - I 1 - I ·,*.0^ - I - . » - _ - (請先閱讀背面之注意事項再填寫本頁) 一異構脫蠟催化劑，包括氧化鋁黏合劑中65% SSZ-32，及包含0.325重量％鉑，其使用程序類似於美國專利權 5，3 76,260號所述。此催化劑指定爲催化劑A。一氫化處理催化劑使用類似美國專利權5,393,408號之程序號製備。氫化處理催化劑包含〇·5重量百分比鉑在包含 66% A12〇3上之矽石-氧化鋁基質上。此催化劑指定爲催化劑B。 -33- 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297公釐〉 A7 —___ 五、發明説明（31 ) 催化劑A( 1 0完升）與具下列各項物理性質之蠟質加氫裂' 解進料一起接觸：氮：3.1毫微克/微升硫：0.005重量％蠟含量：16重量％A7 A7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (28) Each «petroleum component> is separated and treated individually in the isolation operation in the catalytic deaerator reactor 141 containing the catalytic deaeration reaction zone 14Q. The catalytic dewaxing reaction zone 140 contains a layered catalyst system of the present invention. Removal of sulfur and nitrogen, opening of aromatic and aliphatic ring structures, and viscosity index of the rhenium feedstock are included in the first catalyst layer material of the noble metal A-treatment catalyst. The second catalyst layer including the isomerized dewaxing catalyst of the present invention reduces the pour point of the feed after the hydroisomerization reaction. The layered catalyst system layer and the heterogeneous dewaxing catalyst layer produce a low pour point, high yield, and high quality dewaxing base oil. The pour point of the dewaxed oil product 152 from the dewaxing reaction zone 140 desirably has a pour point of less than about 5 ° C, and more preferably less than about 0. (:, And more preferably less than about _5 汜. The method of the present invention can also be combined with traditional dewaxing methods to achieve lubricating oil with special needs. For example, the method of the present invention can be used to reduce the pour point of the lubricating oil to the required degree . Then further reduction of pour point can be achieved by using the traditional dewaxing method. Under this environment, after following the isomerization method of the present invention, the lubricating oil can immediately have a pour point greater than about 15T. Furthermore, the present invention The pour point of the lubricating oil produced by the method can be reduced by adding a pour point inhibitor composition. The effluent from the catalytic de-soiling reaction zone 142 in Fig. 1 contains a de-soiled light oil portion 1 52 and a hydrogen-rich gas stream 1 54. The dewaxing light The oil portion is mixed with a hydrogen-rich gas stream 156, and the hydrogenation catalyst is contacted in a hydrogenation reaction zone 160 contained in the hydrogenation reactor 151. In a preferred example, the entire effluent from the dewaxing reaction zone 142, contacted in the hydrogenation reaction zone 160 with no separation and without adding hydrogen or hydrogen-rich gas, provided that it is sufficient to produce a light lubricant base material 174. The effluent 1 62 from the hydrogenation reaction zone 1 60 is In separation zone 1 70 To separate and recycle the hydrogen-containing gas stream 1 72 for use elsewhere or elsewhere in the refinery -31-This paper rule ^ Applicable to China National Standard (CNS) A4 Specification (210 × 297 Gong Chu Ί): --- 1--I -----I---—1-! · .. | Shishi I. II I-II II — I ι-f— ^ ~~ ·, τ (Please read the notes on the back before filling in this Page) A7 printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ------- B'7__ V. Description of the Invention (29) ~~~ ^ Lubricant base 174 is used as lubricant base for recycling. Hydrogenated The mimicking agent has the activity to improve the storage stability of degreasing oil in the base of lubricating oil. =. Such as removing aromatic compounds, nitrogen and sulfur content and chromosome to a very low / chenity I reaction, This is particularly desirable when minimizing the yield loss of the cracking reaction. The catalyst with a better hydrogenation step comprises a hydrogenation component on the oxide matrix material. The hydrogenation component may be at least a precious metal and / or up to Non-noble metals. Suitable noble metals include platinum, palladium, and other members of the platinum group, such as iridium and ruthenium. Suitable non-noble metals include the periodic table Group VA, VIA, and VIIIA elements. The preferred non-noble metals are chromium, molybdenum, tungsten, cobalt, and nickel and mixtures of these metals, such as nickel-tungsten alloys. Non-noble metal knives can be vulcanized before use, and the temperature is increased. Exposure to sulfur-containing gases, such as hydrogen sulfide, to convert the metal oxide to the corresponding sulfide type. Gasification components can be incorporated into the catalyst by any suitable method, such as by immersion or exchange mixing during the mixing step. Hydrogenation The number of active ingredients can range from about 0.01 to about 45 weight percent and is usually from about 0 "to about 35 weight percent. The exact amount will, of course, change due to the nature of the composition. Less locally active precious metals, especially pins, are more needed than inactive base metals. Preferred hydrogenation catalysts include platinum and / or palladium between 0.1% by weight and 1% by weight on alumina or silica-oxide, including platinum-palladium alloy with platinum-palladium mole The ratio is between about 2 5: i to i ·· 2.5, more preferably between 2: 1 to 1: 1, and optimally equals about i: 1.5. The optimal hydrogenation catalyst has a total pore volume greater than about 0,45 cubic centimeters per gram, more preferably greater than about 0.55 cubic centimeters per gram, and at least about 1%, and more preferably at least about 3%. The total pore volume is greater than about 10 in diameter. 〇〇 Angstrom holes, and most -32- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm)-«»-II. (Please read the notes on the back before filling J7 on this page. Binding. A7 _____ B7 ~ '丨 — V. Description of the invention (3〇) The volume of a small amount of macropores is preferably greater than 0.07 cubic centimeters / gram. When used herein, the term " megapores " also means The catalyst has a large amount of pore volume, that is, at least i% of the pores have a diameter greater than about 1000 Angstroms 'and the smallest macropore volume is more preferably greater than 0.07 cubic centimeters per gram. In Figure 1' a reaction sequence deals with heavy feedstocks, which uses The reference code is 2000 series, which is suitable for the above-mentioned processing of light feed using the reference sequence of 1000 series. To avoid repetition, a detailed description of one of the reaction sequences of heavy lubricant base 274 reaction sequence will not be included here. When the catalyst is used in the corresponding reaction zone (for example The first hydrocracking reaction zone 1 1 0 and the second hydrocracking reaction zone 2 10 and so on) are not necessarily consistent and fall within the catalyst description described herein. Figure 1 illustrates the method to provide a single source The feed passes through the fractionator 10 to the integration method. In practice, the fraction j 02 to the first hydrocracking reaction zone and the fraction 202 to the second hydrocracking reaction zone may come from different sources. Therefore As in the non-limiting example, one of 102 and 202 may come from a tritium gas oil stream, and the other may come from a waxy feed, such as relaxation wax or waxy petroleum feed, to produce a Group III lubricating oil base. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards m J-I----II--_I-I 1-I ·, *. 0 ^-I-. »-_-(Please read the notes on the back before filling (This page) A heterogeneous dewaxing catalyst, including 65% SSZ-32 in alumina binder, and containing 0.325% by weight of platinum, using a procedure similar to that described in US Patent No. 5,3 76,260. This catalyst is designated as the catalyst A. A hydrotreating catalyst uses a procedure similar to US Patent No. 5,393,408 Preparation. Hydrotreating catalyst contains 0.5% by weight platinum on a silica-alumina substrate containing 66% A1203. This catalyst is designated as Catalyst B. -33- This paper size applies Chinese National Standard (CMS) A4 Specifications (210X297 mm) A7 —___ V. Description of the invention (31) Catalyst A (10 liters) is in contact with waxy hydrocracking solution with the following physical properties: Nitrogen: 3.1 nanograms / Microliter sulfur: 0.005% by weight Wax content: 16% by weight

傾點：45°C 黏質在100°C : 11_77厘史托（cSt) 、密度：0.89克/立方公分在23 00磅/平方吋（大氣）總壓力、氫流率237毫升/分鐘、和1 6毫升/小時進料比率。調節反應溫度以產生不同傾點之產品，且脱螺_產品之產率和黏度指數經測定。圖2和3顯示由測試資料之範圍。圖2和3也提供溶劑脫蠟樣品之基線資料。圖4顯示脱壤產品的傾點如何依反應溫度而不同。在相同反應條件下，以催化劑B ( 0.2 5毫升）在催化劑a (0· 75毫升）上之層狀催化劑重複實驗。資料也繪圖在圖2 _ 經濟部中央標準局員工消費合作社印製 (讀先閱讀背面之注意事項再填寫本頁) 4。根據資料，層狀催化劑系統在一定傾點（圖3 )時，產生較南黏度指數之產品，同時在一定的催化活性（圖4 )上維持 • 本質上相寺之產品產率（圖2)。黏度指數之改善在非常低傾點時增加，其中黏度指數未減少，而由催化劑A之產品的黏度指數當傾點減少時減少。 -34- 本纸張尺度適用中國國家標毕（CNS ) A4規格（2丨〇><297公釐）Pour point: 45 ° C Viscosity at 100 ° C: 11_77 centimeters stow (cSt), Density: 0.89 g / cm3 at 23 00 psi (atmospheric) total pressure, hydrogen flow rate 237 ml / min, and 16 ml / h feed ratio. The reaction temperature was adjusted to produce products with different pour points, and the yield and viscosity index of the snail product were determined. Figures 2 and 3 show the range of data from the test. Figures 2 and 3 also provide baseline data for solvent dewaxing samples. Figure 4 shows how the pour point of a desalted product varies depending on the reaction temperature. Under the same reaction conditions, the experiment was repeated with a layered catalyst of catalyst B (0.25 ml) on catalyst a (0.75 ml). The information is also plotted in Figure 2 _ printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (read the precautions on the back before filling out this page) 4. According to the data, at a certain pour point (Figure 3), the layered catalyst system produces products with a southern viscosity index, while maintaining a certain catalytic activity (Figure 4). • Essentially, the product yield of Xiangsi Temple (Figure 2) . The improvement in viscosity index increases at very low pour points, where the viscosity index does not decrease, and the viscosity index of the product from Catalyst A decreases when the pour point decreases. -34- This paper size applies to China National Standard Complete (CNS) A4 specification (2 丨〇 > < 297 mm)

Claims

第ξΤΠΐ49㈣專利申Κ爲 • S __圍_遽表(89年5月)The ξΤΠΤ49㈣ patent application is: S __ 围 _ 遽表 (May 89)

經濟部中央標隼局員工消費合作社印製了研弱f範圍 1. 一種潤滑油烴類處理方法，其涉及一序列步驟：氫化處理以除去異類原子及至少一部分芳族，然後氫化處理/加氫裂解以將芳族化合物飽和化、異構化及黏度指數升級，然後加氫異構化以移除蠟類及最後加氫完成以獲得潤滑油穩定性，第二階段加氫裂解之較優方法包含：反應器裡的第一催化劑及其上層覆之第二催化劑，該第一催化劑包括異構脫蠟催化劑；及於該反應器中第一催化劑層上之第二催化劑層，該第二催化劑選自包含下列族群中：貴金屬非晶態催化劑、貝金屬加氧裂解催化劑、或其組合物，且其中該第一及第二催化劑組合物’在基礎潤滑油製造時，比起單一反應器裝以單一之該第一催化劑而言，在給定黏度指數下，達成較長催化劑壽命及較高活性和較高產率。 2. 根據申請專利範圍第i項之方法’其中該異構脫蠟催化劑包含中值孔分子篩，其具微晶尺寸不大於〇.5微米，且具孔隙之最小孔隙直徑至少4_8埃及最大孔隙直徑不大於 7.1埃，該催化劑： a) 具足夠酸性’而使其0.5克當在370 °C溫度、.壓力 1200磅/平方吋（大氣）、氫氣流16〇毫升/分鐘及進料速率 1毫升/小時的條件下放置於1 / 4叶内徑管反應器時，至少轉換50%十六烷，及 b) 具40或更大之同分異構化選擇性，其定義為：產品中分枝C[6重量％ -----___X 100 產品中分枝C!6重量。/。+產品中C13重量〇/〇 : 裝訂厶π (請先聞讀背面之注意事項再填寫本頁) 本紙張尺;f诚用中SllSt古4*地/Μ、千 ί I ί * «·The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs has printed a range of research f. 1. A method for treating lubricating oil hydrocarbons, which involves a series of steps: hydrogenation treatment to remove heterogeneous atoms and at least a part of aromatics, and then hydrogenation treatment / hydrogenation Pyrolysis to saturate, isomerize and viscosity index of aromatic compounds, then hydroisomerize to remove waxes and final hydrogenation is completed to obtain lubricating oil stability. A better method for hydrocracking in the second stage It comprises: a first catalyst in a reactor and a second catalyst overlying the first catalyst, the first catalyst including an isomerized dewaxing catalyst; and a second catalyst layer on the first catalyst layer in the reactor, the second catalyst Is selected from the group consisting of a noble metal amorphous catalyst, a shell metal oxygenation cracking catalyst, or a combination thereof, and wherein the first and second catalyst compositions are compared with a single reactor when manufacturing base lubricants For a single such first catalyst, at a given viscosity index, a longer catalyst life, higher activity and higher yield are achieved. 2. The method according to item i of the scope of the patent application, wherein the heterogeneous dewaxing catalyst comprises a median pore molecular sieve having a crystallite size of not more than 0.5 micron and a minimum pore diameter of at least 4-8 Egyptian maximum pore diameter Not more than 7.1 Angstroms, the catalyst: a) is sufficiently acidic to make it 0.5 grams when at a temperature of 370 ° C, a pressure of 1200 psi (atmospheric), a hydrogen flow of 16 ml / min and a feed rate of 1 ml When placed in a 1 / 4-leaf inner diameter tube reactor under conditions of 1 / hour, at least 50% of hexadecane is converted, and b) has an isomerization selectivity of 40 or more, which is defined as: Branch C [6% by weight -----___ X 100 branch C! 6 weight in the product. /. + C13 weight in the product 〇 / 〇: Binding 厶 π (Please read the precautions on the back before filling in this page) This paper ruler; f Sincere use SllSt ancient 4 * place / Μ, thousand ί I ί * «·

經濟部中央標隼局員工消費合作社印製了研弱f範圍 1. 一種潤滑油烴類處理方法，其涉及一序列步驟：氫化處理以除去異類原子及至少一部分芳族，然後氫化處理/加氫裂解以將芳族化合物飽和化、異構化及黏度指數升級，然後加氫異構化以移除蠟類及最後加氫完成以獲得潤滑油穩定性，第二階段加氫裂解之較優方法包含：反應器裡的第一催化劑及其上層覆之第二催化劑，該第一催化劑包括異構脫蠟催化劑；及於該反應器中第一催化劑層上之第二催化劑層，該第二催化劑選自包含下列族群中：貴金屬非晶態催化劑、貝金屬加氧裂解催化劑、或其組合物，且其中該第一及第二催化劑組合物’在基礎潤滑油製造時，比起單一反應器裝以單一之該第一催化劑而言，在給定黏度指數下，達成較長催化劑壽命及較高活性和較高產率。 2. 根據申請專利範圍第i項之方法’其中該異構脫蠟催化劑包含中值孔分子篩，其具微晶尺寸不大於〇.5微米，且具孔隙之最小孔隙直徑至少4_8埃及最大孔隙直徑不大於 7.1埃，該催化劑： a) 具足夠酸性’而使其0.5克當在370 °C溫度、.壓力 1200磅/平方吋（大氣）、氫氣流16〇毫升/分鐘及進料速率 1毫升/小時的條件下放置於1 / 4叶内徑管反應器時，至少轉換50%十六烷，及 b) 具40或更大之同分異構化選擇性，其定義為：產品中分枝C[6重量％ -----___X 100 產品中分枝C!6重量。/。+產品中C13重量〇/〇 : 裝訂厶π (請先聞讀背面之注意事項再填寫本頁) 本紙張尺;f诚用中SllSt古4*地/Μ、千 ί I ί * «· 經濟部中央揉準局貝工消費合作杜印製 AS B8 C8 ----------- --D8 _ __ 六、申請專利範圍一當在條件下使用時導致十六烷之96%轉化率。 3·根據申請專利範圍第1項之方法，其中該異構脫蠟催化劑包含潍石’其選自包含下列族群中：23]^_5、23]^-12、ZSM-21、ZSM-22、ZSM-23、ZSM-35、ZSM-38、 ZSM_57、矽鉀鋁石、鎂鈉針沸石和SUZ-4。 4.根據申請專利範圍第1項之方法，其中該異構脫蠟催化劑包含沸石為選自包含下列族群中：SSZ-31、SSZ-32、 SSZ-36 及 SSZ-41。 5·根據申請專利範圍第1項之方法，其中該異構脫蠟催化劑包含非沸石分子篩為選自包含下列族群中：SAP0-11、 SAP0-31、SAPO-41、MAP0-11 和MAP0-31。 6. 根據申請專利範圍第1項之方法，其中該第二催化劑為貴金屬非晶態催化劑包括〇. 1至1重量百分比之間貴金屬氫化作用和非晶態基質材料。 7. 根據申請專利範圍第6項之方法，其中該貴金屬氫化作用成分為選自包含下列族群中：鉑、鈀或其混合物，且其中該非晶態基質材料包含矽石-氧化鋁。 8. 根據申請專利範園第7項之方法，其中該第二催化劑包含銘-免合金和Si〇2/Al2〇3氧化物基質，而其中該合金中銘對鈀之莫耳比是介於2.5 : 1至1 : 2.5之間。 9. 根據申請專利範圍第1項之方法，其中該第二催化劑為貴金屬加氫裂解催化劑包括在〇. 1和1重量百分比之間貴金屬氫化作用成分及由〇 · 1到2 0重量百分比沸石，其選自包含下列族群中：八面沸石、沸石Y和超穩沸石Y。 -2- 本紙張尺度逋用中國國家樣準（CNS ) A4規格（210X297公釐) '' 11 I n ' . n I n n I -訂--11 -¾¾ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 A8 B8 C8 __D8六、申請專利範圍 ίο. —種生產潤滑油基料之方法，其包含在反應器内第一催化劑上，於脫蠟及氫化處理條件下，以氫接觸蠟質油，第一催化劑其上層覆第二催化劑，該第一催化劑包括異構脫蠟催化劑且於該反應器中第一催化劑層上之第二催化劑層，該第二催化劑選自包含下列族群中：貴金屬非晶態催化劑、貴金屬加氫裂解催化劑、或其組合物以產生脫蠟油；其中該第一及第二催化劑組合物，在基礎潤滑油製造時，比起單一反應器裝以單一之該第一催化劑而言，在給定脫蟻油傾點下，連成較長催化劑壽命及較高黏度指數及較高產率。 11·根據申請專利範園第1 〇項之方法，其中該第二催化劑包含在Si02/Al203支載物上的Pt及/或Pd。 12. 根據申請專利範圍第1 〇項之方法，其中該第二催化劑包含始-免合金及Si02/Al203氧化物基質，而其.中該合金裡鉑對鈀的莫耳比是介於2.5 : 1至1 : 2.5之間。 13. 根據申請專利範圍第1 〇項之方法，其中該異構脫蠟催化劑包含中值孔分子篩’其具微晶尺寸不大於〇.5微米，且具孔隙之最小孔隙直徑至少4.8埃及最大孔隙直徑不大於 7.1埃，該催化劑： a) 具足夠酸性，而使其〇.5克當在370 t溫度、壓力 1200磅/平方吋（大氣）、氫氣流16〇毫升/分鐘及進料速率 1毫升/小時的條件下放置於丨/4吋内徑管反應器時，至少轉換50%十六烷，及 b) 具40或更大之同分異構化選擇性，其定義為： -3· $張逋用中國國家棣準CNS )八4祕（21〇><297公董） -— III — - .訂氣 (請先閱讀背面之注意事項再填寫本頁)The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs has printed a range of research f. 1. A method for treating lubricating oil hydrocarbons, which involves a series of steps: hydrogenation treatment to remove heterogeneous atoms and at least a part of aromatics, and then hydrogenation treatment / hydrogenation Pyrolysis to saturate, isomerize and viscosity index of aromatic compounds, then hydroisomerize to remove waxes and final hydrogenation is completed to obtain lubricating oil stability. A better method for hydrocracking in the second stage It comprises: a first catalyst in a reactor and a second catalyst overlying the first catalyst, the first catalyst including an isomerized dewaxing catalyst; and a second catalyst layer on the first catalyst layer in the reactor, the second catalyst Is selected from the group consisting of a noble metal amorphous catalyst, a shell metal oxygenation cracking catalyst, or a combination thereof, and wherein the first and second catalyst compositions are compared with a single reactor when manufacturing base lubricants For a single such first catalyst, at a given viscosity index, a longer catalyst life, higher activity and higher yield are achieved. 2. The method according to item i of the scope of the patent application, wherein the heterogeneous dewaxing catalyst comprises a median pore molecular sieve having a crystallite size of not more than 0.5 micron and a minimum pore diameter of at least 4-8 Egyptian maximum pore diameter Not more than 7.1 Angstroms, the catalyst: a) is sufficiently acidic to make it 0.5 grams when at a temperature of 370 ° C, a pressure of 1200 psi (atmospheric), a hydrogen flow of 16 ml / min and a feed rate of 1 ml When placed in a 1 / 4-leaf inner diameter tube reactor under conditions of 1 / hour, at least 50% of hexadecane is converted, and b) has an isomerization selectivity of 40 or more, which is defined as: Branch C [6% by weight -----___ X 100 branch C! 6 weight in the product. /. + C13 weight in the product 〇 / 〇: Binding 厶 π (please read the precautions on the back before filling this page) This paper ruler; f Sincere use SllSt ancient 4 * place / Μ, Qian I I ί * «Economic The Central Government Bureau of the Ministry of Industry and Commerce of the United States Shellfish Consumer Cooperation Du printed AS B8 C8 ----------- --D8 _ __ VI. Scope of patent application-96% of cetane when used under conditions Conversion rate. 3. The method according to item 1 of the scope of patent application, wherein the isomerized dewaxing catalyst comprises Weishi 'which is selected from the group consisting of: 23] ^ _ 5, 23] ^-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM_57, wollastonite, magnesite and SUZ-4. 4. The method according to item 1 of the application, wherein the isomerized dewaxing catalyst comprises zeolite selected from the group consisting of SSZ-31, SSZ-32, SSZ-36 and SSZ-41. 5. The method according to item 1 of the scope of patent application, wherein the heterogeneous dewaxing catalyst comprises a non-zeolitic molecular sieve selected from the group consisting of: SAP0-11, SAP0-31, SAPO-41, MAP0-11 and MAP0-31 . 6. The method according to item 1 of the patent application scope, wherein the second catalyst is a noble metal amorphous catalyst comprising between 0.1 and 1 weight percent of noble metal hydrogenation and an amorphous matrix material. 7. The method according to item 6 of the application, wherein the noble metal hydrogenation component is selected from the group consisting of platinum, palladium or a mixture thereof, and wherein the amorphous matrix material comprises silica-alumina. 8. The method according to item 7 of the patent application park, wherein the second catalyst comprises a Ming-free alloy and a Si〇2 / Al203 oxide matrix, and wherein the molar ratio of Ming to palladium in the alloy is between 2.5: 1 to 1: 2.5. 9. The method according to item 1 of the scope of patent application, wherein the second catalyst is a precious metal hydrocracking catalyst comprising a precious metal hydrogenation component between 0.1 and 1 weight percent and a zeolite from 0.1 to 20 weight percent, It is selected from the group consisting of faujasite, zeolite Y, and metastable zeolite Y. -2- This paper size uses China National Standard (CNS) A4 size (210X297 mm) '' 11 I n '. N I nn I -Order--11 -¾¾ (Please read the notes on the back before filling (This page) Printed A8 B8 C8 __D8 by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 6. Application for patents. A method for producing lubricant base materials, which is included in the first catalyst in the reactor. Under the condition of hydrogenation treatment, the waxy oil is contacted with hydrogen, and the first catalyst layer is covered with a second catalyst. The first catalyst includes an isomerized dewaxing catalyst and a second catalyst layer on the first catalyst layer in the reactor. The second catalyst is selected from the group consisting of a noble metal amorphous catalyst, a noble metal hydrocracking catalyst, or a combination thereof to produce a dewaxed oil; wherein the first and second catalyst compositions are used in the manufacture of base lubricants, Compared with a single reactor equipped with a single first catalyst, for a given determinant oil pour point, a longer catalyst life, a higher viscosity index and a higher yield are obtained. 11. The method according to item 10 of the patent application park, wherein the second catalyst contains Pt and / or Pd on a Si02 / Al203 support. 12. The method according to item 10 of the scope of patent application, wherein the second catalyst comprises a starting-free alloy and a Si02 / Al203 oxide matrix, and wherein the molar ratio of platinum to palladium in the alloy is between 2.5: 1 to 1: 2.5. 13. The method according to item 10 of the scope of patent application, wherein the heterogeneous dewaxing catalyst comprises a median pore molecular sieve having a crystallite size of not more than 0.5 micron and a minimum pore diameter of at least 4.8 and a maximum pore of Egypt. The diameter is not greater than 7.1 Angstroms. The catalyst: a) is sufficiently acidic to make 0.5 grams when it is at a temperature of 370 t, a pressure of 1200 psi (atmospheric), a hydrogen flow of 16 ml / min and a feed rate of 1 When placed in a 4-inch ID tube reactor under the condition of ml / h, at least 50% of hexadecane is converted, and b) it has an isomerization selectivity of 40 or more, which is defined as: -3 · $ 张逋用中国国准准 CNS) The Eighth Secret (21〇 > < 297 Public Director)--III--. Reservation (please read the precautions on the back before filling this page)

申請專利範圍產品中分枝c 16重量％ JC100 經濟部中央標隼局員工消費合作社印製產品中分枝(：“重量❶/^十產品中c13重量％當在條件下使用時導致十六烷之96%轉化率。 14·根據申請專利範圍第10項之方法，其中該蠟質油為來自加氫裂化器反應區之蠟質氫化裂解物。 15·根據申請專利範圍第14項之方法，其中該蠟質油在溶劑脫壤基準上具黏度指數至少80。根據申請專利範圍第丨4項之方法脫壤基準上具黏度指數至少9 5。口.根據申請專利範圍第1 4項之方法劑脫蠟基準上具黏度指數至少i 10 队根據申請專利範圍第丨〇項之方法反應溫度介於由550T到850°F的範圍、反應壓力介於由 1 5嗓/平方吋（大氣）到3 500磅/平方吋（大氣）的範圍、及進料速率介於由〇. 1到2 0 /小時的範圍内。根據申請專利範圍第1 〇項之方法，進一步包括在該貴金屬氫化作用催化劑之上於氫化作用反應條件下以氫接觸脫蠟石油基料以產生潤滑油基料。 2〇_根據申請專利範圍第1 9項之方法，其中該潤滑油基料為弟11族油。 21. 根據申請專利範圍第1 9項之方法，其中該潤滑油基料為第III族油。 22. 根據申請專利範圍第1 〇項之方法，其中該蠟質油包含大於5 0 %峨。其中該蠟質油在溶劑其中該蠟質石油在溶其是在反應條件包括 (請先閱讀背面之注意事項再填寫本買) .柒· -Γ W . -V3 Γ -4 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）Patent application scope Branch 16% by weight in product JC100 Branch in printed products printed by employees of the Central Bureau of Standards of the Ministry of Economic Affairs (: "weight ❶ / ^ 10% by weight of product c13% when used under conditions) Conversion rate of 96%. 14. The method according to item 10 of the scope of the patent application, wherein the waxy oil is a waxy hydrogenation cracker from the reaction zone of a hydrocracker. 15. The method according to item 14 of the scope of patent application, Wherein, the waxy oil has a viscosity index of at least 80 on the basis of solvent de-soiling. According to the method of the scope of application for patents, the viscosity index is at least 9 5. The dewaxing agent has a viscosity index of at least i 10. The reaction temperature ranges from 550T to 850 ° F, and the reaction pressure ranges from 15 vocals per square inch (atmospheric) to The range of 3,500 psi (atmospheric) and the feed rate range from 0.1 to 20 / hour. The method according to item 10 of the patent application range further includes the noble metal hydrogenation catalyst Under the hydrogenation reaction conditions above, the dewaxed petroleum base material is contacted with hydrogen to produce a lubricating oil base material. 20_ The method according to item 19 of the patent application scope, wherein the lubricating oil base material is a Group 11 oil. 21 The method according to item 19 of the scope of patent application, wherein the lubricating base is a Group III oil. 22. The method according to item 10 of the scope of patent application, wherein the waxy oil contains more than 50% e. The waxy oil is in the solvent. The waxy oil is soluble. The reaction conditions are included (please read the precautions on the back before filling in this purchase). 柒 · -Γ W. -V3 Γ -4 This paper size applies to China Standard (CNS) Α4 specification (210X297 mm)

申請專利範圍經濟部中央橾隼局員工消費合作社印裝 23. :種製備多數潤滑油基料之整合方法，而該基料是以彼、之間的黏度區分’其中根據申請專利範圍第W項之方法為同時地在至少二分開及平行序列中進行。 24. -種由石油進料中產生多數澗滑油基料之整合方法，該方法包含： a) 分開石油進料成至少_個輕餾份流及至少一個重餾份流 b) 產生至少一輕質潤滑油基料之方法，其包括： i)在加氫裂解反應條件足以將至少硫之部分及至少氮之部^由輕餾份流中移開下，以第—加氫裂解反應區裡之氫接觸至少一輕餾份流，而產生至少一個蠟質輕油組份’其具黏度指數相對於輕餾份流之黏度指數而言為增加 H)用第一脫蠟反應區中氫接觸至少一蠟質輕油組份，該反應區包括層狀催化劑系統，其包含第一催化劑及層覆其上之弟二低化劑，第一催化劑包括異構脫蠟催化劑而第二催化劑選自包含下列族群中：貴金屬非晶態.催化劑、貴金屬加氫裂解催化劑、或其組合物；及 iii)在足以產生輕質潤滑油基料條件下在氫化作用反應區接觸至少部分第一個脫蠟反應區流出物；及 c) 產生至少一重潤滑油基料之方法，其包括： i)在條件足以將至少硫之部分及至少氮之部分由重餾份流中移開下，以第二加氫裂解反應區裡之氣接觸 -5- 本紙張尺度適用中國國家梯準（CNS ) A4规格（210X297公釐） I----:~~„--^---裝------—訂--------線 C請先聞讀背面之注意事項再填寫本頁} 經濟部中央樣準局員工消費合作社印製 A8 B8 C8 D8 ----—----- 六、申請專利範園至少一重餾份流’而產生至少一蠟質重油組份，其具黏度指數相對於重餾份流之黏度指數而言為增加； H)用第二脫蠟反應區中氫接觸至少一蠟質重油組份’該反應區包括層狀催化劑系巍，其包含第三催化劑及層覆其上之第四催化劑，第三催化劑包括異構脫蠟催化劑而第四催化劑選自包含下列族群中：貴金屬非晶態催化劑、貴金屬加氫裂解催化劑、或其組合物；及 iii)在足以產生重質潤滑油基料條件下在氫化作用反應區接觸至少部分第二個脫蠟反應區流出物，其中該產生至少一輕質潤滑油基料的方法及產生至少一個重質潤滑油基料的方法為在平行反應序列中同時地進行。 25·根據申請專利範圍第2 4項之方法，其中該輕質潤滑油基料為第II族油’且重潤滑油基料為第Η族油。 26_根據申請專利範圍第2 5項之方法，其中該輕質澗滑油基料為第III族油。 27·根據申請專利範圍第2 5項之方法，其中該重質潤滑油基料為第III族油。 28. 根據申請專利範圍第2 6項之方法，其中該重質潤滑油基料為第III族油。 29. 根據申請專利範圍第2 4項之方法，其中該第一反應區中異構脫蠟催化劑為選自SSZ-31、SSZ-32、SSZ-36和SSZ-41 〇 -6 - 本紙張逋用中國國家揉準（CNS } Α規^ ( 21〇Χ297公釐）—"" (請先閱讀背面之注意事項存填寫本貰) -装· 訂線 AS B8 C8 D8 經濟部_央榡準局貝工消費合作社印製申請專利範圍 3〇.根據申請專利範圍第24項之方法，其中該第一反應區中異構脫環催化劑為選自SApo」i、SAP0-3 1和SAP0-41。 31_根據申請專利範圍第24項之方法，其中該蠟質氫化裂解物包含少於1〇〇百萬分之一硫且包含少於5〇百萬分之一氮。 32. 根據申請專利範園第3 i項之方法，其中該蠟質氫化裂解物包含少於25百萬分之一硫且包含少於10百萬分之一氮。 33. 根據申請專利範圍第2 4項之方法，其中該氫化作用催化 Μ為貝金屬非晶態催化劑，其包括在〇 . 1至1重量百分比之貴金屬氫化作用和非晶態基質材料。 34. 根據申請專利範圍第3 3項之方法，其中該貴金屬氫化作用成分為選自包含下列族群中：鉑、麵或其混合物，且其中該非晶態基質材料包含矽石-氧化鋁。 35_根據申請專利範圍第3 3項之方法，其中該氫化作用催化劑包含舶-細合金和Si〇2/Al2〇3氧化物基質，而其中該合金中舶對鈀之莫耳比是介於2_5:1至1:25之間。 36_根據申諳專利範圍第2 4項之方法，其中整個該第 > 脫蠟反應區流出物為在氫化作用反應區裡與氫接觸。 37. 根據申請專利範圍第2 4項之方法，其中整個該第二脱蠟反應區流出物為在氫化作用反應區裡與氫接觸。 38. —種產生脫蠟石油之精煉操作方法，且具至少一脫蠟反應區包含異構脫蠟催化劑以降低蠟質油之傾點，該方法包括： I-----j!-裝-----訂------線 (請先閱讀背面之注意事項再填寫本頁) A«sD-8 S99092 #、申請專利範圍 a) 於該反應器中至少一脫蠟反應區中包含在異構脫壤催化劑頂端之第二催化劑層，催化劑為該第二催化劑層遠自包含下列族群中·貴金屬非晶態催化劑、貴金屬加氫裂解催化劑或其組合物； b) 以風與該堪質油在該第二催化劑層上接觸. c) 接觸由異構脫蠟催化劑上第二催化劑層之全體流出物和 d) 回收脫蠟油’其具傾點比蠟質油相較而言為降低。 39. 根據申請專利範圍第3 8項之方法，其中該蠟質法具介於 260°C至650°C範圍内之沸點。 ;、 40. 根據申請專利範園第38項之方法’其中該脫蠟油之傾點低於-5°C。 4L -種製備多數潤滑油基料之整合方法，而該基料是以彼此之間的黏度區分，其中根據申請專利範圍第38項之方法為同時地在至少二分開及平行序列中進行。 I ^ „ . ‘裝訂^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標率局員工消費合作社印製 -8，本紙張尺度逋用中國國家標準（CNS ) A4規^ ( 210X297公董~~ --Patent Application Scope: Printed by the Consumer Affairs Cooperative of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China 23 .: An integrated method for preparing most lubricating oil base materials, and the base materials are distinguished by their viscosity, among which according to the W This is done simultaneously in at least two separate and parallel sequences. 24. An integrated method for generating most of the base oil base in a petroleum feed, the method comprising: a) separating the petroleum feed into at least one light ends stream and at least one heavy ends stream b) generating at least one A method for a lightweight lubricating oil base material, comprising: i) removing at least a portion of sulfur and at least a portion of nitrogen ^ from a light ends stream under a hydrocracking reaction condition to a first hydrocracking reaction zone The hydrogen in the contact with at least one light ends stream to produce at least one waxy light oil component 'has a viscosity index that increases relative to the viscosity index of the light ends stream.H) The hydrogen in the first dewaxing reaction zone is used. In contact with at least one waxy light oil component, the reaction zone includes a layered catalyst system including a first catalyst and a second reducing agent layered thereon. The first catalyst includes an isomerized dewaxing catalyst and the second catalyst is selected. From the group consisting of: noble metal amorphous. Catalyst, noble metal hydrocracking catalyst, or a combination thereof; and iii) contacting at least a portion of the first dehydration in a hydrogenation reaction zone under conditions sufficient to produce a light lubricant base material. Wax reaction zone flow And c) a method for producing at least one heavy lubricant base, comprising: i) removing the at least a portion of sulfur and at least a portion of nitrogen from a heavy distillate stream under conditions sufficient to perform a second hydrocracking reaction Air contact in the area -5- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) I ----: ~~ „-^ ------------------ Order -------- Line C, please read the precautions on the back before filling out this page} Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 ------------ Apply for a patent for at least one heavy distillate stream to produce at least one waxy heavy oil component, the viscosity index of which is increased relative to the viscosity index of the heavy distillate stream; H) contact with hydrogen in the second dewaxing reaction zone At least one waxy heavy oil component. The reaction zone includes a layered catalyst system including a third catalyst and a fourth catalyst layered thereon. The third catalyst includes an isomerized dewaxing catalyst and the fourth catalyst is selected from the group consisting of In the group: noble metal amorphous catalyst, noble metal hydrocracking catalyst, or a combination thereof; and iii) in the foot Contacting at least part of the effluent from the second dewaxing reaction zone in the hydrogenation reaction zone under conditions of producing heavy lubricating oil base material, wherein the method for producing at least one light lubricating oil base material and producing at least one heavy lubricating oil base material The method is carried out simultaneously in a parallel reaction sequence. 25. The method according to item 24 of the patent application scope, wherein the light lubricating oil base is a Group II oil and the heavy lubricating oil base is a Group VIII oil 26_ The method according to item 25 of the scope of the patent application, wherein the light weight base oil is a Group III oil. 27. The method according to the item 25 of the scope of patent application, wherein the heavy lubricant base material Group III oil. 28. The method according to item 26 of the patent application, wherein the heavy lubricant base is a Group III oil. 29. The method according to item 24 of the scope of patent application, wherein the isomerization dewaxing catalyst in the first reaction zone is selected from the group consisting of SSZ-31, SSZ-32, SSZ-36, and SSZ-41 〇-6-This paper 逋Use the Chinese national standard (CNS) Α ^^ (21〇 × 297mm)-" " (Please read the precautions on the back and fill in this card)-Assembly · Thread AS B8 C8 D8 Ministry of Economic Affairs_central The quasi-station Shellfish Consumer Cooperative printed the scope of patent application 30. The method according to item 24 of the scope of patent application, wherein the isomerization deringing catalyst in the first reaction zone is selected from SApo''i, SAP0-3 1 and SAP0- 41. 31_ The method according to item 24 of the scope of patent application, wherein the waxy hydrogenated pyrolysate contains less than 100 parts per million sulfur and contains less than 50 parts per million nitrogen. 32. According to the application The method of item 3 i of the patent park, wherein the waxy hydrogenated pyrolysate contains less than 25 parts per million of sulfur and contains less than 10 parts per million of nitrogen. 33. According to item 24 of the scope of patent application Method, wherein the hydrogenation catalyst M is a shell metal amorphous catalyst, which comprises between 0.1 to 1 weight percent Noble metal hydrogenation and amorphous matrix material. 34. The method according to item 33 of the patent application scope, wherein the noble metal hydrogenation component is selected from the group consisting of platinum, noodles or mixtures thereof, and wherein the amorphous state The matrix material comprises silica-alumina. 35_ The method according to item 33 of the patent application scope, wherein the hydrogenation catalyst comprises a ferrite-fine alloy and a Si〇2 / Al203 oxide matrix, and wherein the alloy contains The molar ratio to palladium is between 2_5: 1 and 1:25. 36_ The method according to item 24 of the patent application, wherein the effluent of the > dewaxing reaction zone is reacted in a hydrogenation reaction The zone is in contact with hydrogen. 37. The method according to item 24 of the patent application scope, wherein the entire effluent of the second dewaxing reaction zone is in contact with hydrogen in the hydrogenation reaction zone. 38. A type of dewaxed petroleum A refining operation method with at least one dewaxing reaction zone containing an isomerized dewaxing catalyst to reduce the pour point of a waxy oil. The method includes: I ----- j!-装 ----- Order --- --- line (please read the precautions on the back before filling this page) A sD-8 S99092 #, patent application scope a) In the reactor, at least one dewaxing reaction zone includes a second catalyst layer on top of the heterogeneous de-soiling catalyst, and the catalyst is a second catalyst layer far from the following groups A noble metal amorphous catalyst, a noble metal hydrocracking catalyst, or a combination thereof; b) contacting the keratin oil with the wind on the second catalyst layer; c) contacting the second catalyst layer on the isomerized dewaxing catalyst The overall effluent and d) recovered dewaxed oil 'has a pour point which is lower than that of waxy oil. 39. The method according to item 38 of the scope of patent application, wherein the waxy method has a boiling point in the range of 260 ° C to 650 ° C. ;, 40. The method according to item 38 of the patent application garden, wherein the pour point of the dewaxed oil is lower than -5 ° C. 4L-An integrated method for preparing most lubricating oil base materials, and the base materials are distinguished from each other by viscosity, in which the method according to item 38 of the patent application is performed simultaneously in at least two separate and parallel sequences. I ^ „. 'Binding ^ (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -8, This paper is in accordance with Chinese National Standard (CNS) A4 ^ (210X297 Director ~~-