TW201121651A - Catalysts for making ethanol from acetic acid - Google Patents

Abstract

Catalysts and processes for forming catalysts for use in hydrogenating acetic acid to form ethanol. In one embodiment, the catalyst comprises a first metal, a silicaceous support, and at least one metasilicate support modifier. Preferably, the first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten. In addition the catalyst may comprise a second metal preferably selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel.

Description

201121651 四、 指定代表圖： (一) 本案指定代表圖為：第（1)圖。 (二) 本代表圖之元件符號簡單說明：無 五、 t案若有化學式時’請揭示最能顯示發明特徵的化學式. 六、 發明說明： 【優先權及相關參考】 本發明主張優先權在於2_年26日提出之美國專利申往案第 職8,727號，及於謂年2月2日提出之美國專利巾請案第u職侧 號’此等專利申請案之整本說明書均可在此做為參考。 ’ 【發明所屬之技術領域】 本發明一般涉及用於醋酸氫化形成乙醇製程之觸媒，本觸媒對乙 高選擇率。 〃 【先前技術】 長期以來認為需要一個種將醋酸變成乙醇之經濟上可行的製程和觸 媒，乙醇可用於它自[的領域或轉作乙稀·一種重要商品的原料，因為 匕可以轉化為醋酸乙烯酯和/或醋酸乙酯或任何各種各樣的其他化學產 物。例如，乙烯也可以轉換為眾多的聚合物和單體產物。波動天然氣和 原油價格造成源自石油或天然氣之乙歸轉統方式生產成本波動，使得 當石油價格上漲時，其他來源的乙烯之需求大增。 還原烷酸(alkanoic acids)和其他羰基化合物的催化製程已被廣泛的研 究，而各種組合的觸媒’支撐體和操作條件在文獻中已被提及。τ Yokoyama等氏在••藉由雜相催化之精細化學品_叛酸及其衍生物"文中評 論藉由金屬氧化物，使各種羧酸還原之方法。在該文中第831節，總 2 201121651 結各種羧酸所用的氫化觸媒之一些進展。（Yokoyama，τ ; Setoyama，τ : “藉由雜相催化之精細化學品，，中之“羧酸及其衍生物，，，2001年， 370-379 頁）。 Μ. A_ Vannice等氏藉由各種雜相觸媒針對醋酸轉化做一系列的研究 (Rachmady W. , Vannice, M. A. J· Ca/dV觸媒期孑ι|)，2002 年，207 期， 317-330頁）。在另一項研究報告中，記載藉由承載及不承載之鐵，使得 醋酸氫化在氣相還原（Rachmady, W. ; Vannice, M. A.，J. Catal，2002 年，208期，158-169頁）。進一步有關觸媒表面物種和有機中間體的資 料 5己載於 Rachmady, W.; Vannice, M. A. ’ J. Catal，2002 年，208 期，170-179 頁。Rachmady，W. ; Vannice，Μ· Α·等氏藉由一系列的承載之鉑-鐵觸 媒進一步研究醋酸氣相氫化，參閱J. Catal ’ 2002年，209期，87-98頁。 Vannice，Μ_Α·氏，J. Catal，2000 年，192 期，322-334 頁。 關於不飽和醛選擇率氫化之各種相關出版物有：Djerb〇ua，F ; Benachour， Ό.; Touroude，R·等氏，Applied Catalvsis.r 應用催化期千Π A :概論，2005 年 ’ 282 期，123-133 頁；Liberkova，K.; Tourounde，R.等氏，Mol. CataU^ 土ifeiyi刊），2002 年，180 期，221-230 頁；Rodrigues，E. L. ; Bueno, J. M. C.等氏，Applied Catalysis. A :概論，2004 年，257 期，210-211 頁； Ammari，F. ; Lamotte，J. ; Touroude, R.等氏，Applied Catnly^Q，2004 年，221 期 ’ 32-42 頁；Ammari，F.; Milone，C.; Touroude，R.等氏，j. Cata卜 2005 年，235 期，1 -9 頁；Consonni，M.; Jokic，D.; Murzin，D. Υ·; Touroude, R·，LM，1999 年，188 期，165-175 頁；Nitta，Y. ·，Ueno, K. ·，lmanaka， T·等氏，Applied Catal.，1989 年，56 期，9-22 頁。 藉由含钻，麵，錫之觸媒，使巴豆酸(crotonaldehyde)選擇性氫化成為 不飽和醇的製法可參閱R· Touroude等氏之研究報告：Djerbc)ua，F ; Benachour，D. ; Touroude, R.等氏，Applied Catalysis A :概論，2〇〇5 年， 282 期，123-133 頁；及 Liberkova，K. ; Tourounde，i?·等氏，.Applied Catalysis，20〇2 年，180 期，221-230 頁；以及 K. Lazar 等氏尤，· 201121651201121651 IV. Designated representative map: (1) The representative representative of the case is: (1). (2) A brief description of the symbol of the representative figure: If there is a chemical formula, there is no chemical pattern of the case. Please disclose the chemical formula that best shows the characteristics of the invention. VI. Description of the invention: [Priority and related references] The US patent application case No. 8,727 filed on February 26th, and the US patent application file filed on February 2nd, the second job title of the patent application can be This is for reference. TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a catalyst for hydrogenation of acetic acid to form an ethanol process, the catalyst having a high selectivity to B. 〃 [Prior Art] It has long been recognized that there is a need for an economically viable process and catalyst for converting acetic acid into ethanol. Ethanol can be used as a raw material from [the field or to ethylene, an important commodity, because hydrazine can be converted into Vinyl acetate and / or ethyl acetate or any of a wide variety of other chemical products. For example, ethylene can also be converted to a wide variety of polymers and monomer products. Fluctuating natural gas and crude oil prices cause fluctuations in the production costs of oil or natural gas, which causes the demand for ethylene from other sources to increase as oil prices rise. Catalytic processes for the reduction of alkanoic acids and other carbonyl compounds have been extensively studied, and various combinations of catalyst' supports and operating conditions have been mentioned in the literature. τ Yokoyama et al. • The method of reducing various carboxylic acids by metal oxides by means of heterogeneously catalyzed fine chemicals _ tickic acid and its derivatives. In Section 831 of this paper, total 2 201121651 knots some progress in the hydrogenation catalysts used in various carboxylic acids. (Yokoyama, τ; Setoyama, τ: "Fine Chemicals by Heterogeneous Catalysis," Carboxylic Acids and Their Derivatives, 2001, pp. 370-379). A. A_ Vannice et al. conducted a series of studies on acetic acid conversion by various heterogeneous catalysts (Rachmady W., Vannice, MA J· Ca/dV Catalyst 孑ι|), 2002, 207, 317- 330 pages). In another study, hydrogenation of acetic acid in the gas phase was carried out by carrying and unsupporting iron (Rachmady, W.; Vannice, MA, J. Catal, 2002, 208, pp. 158-169). . Further information on catalyst surface species and organic intermediates is contained in Rachmady, W.; Vannice, M. A. ’ J. Catal, 2002, 208, pp. 170-179. Rachmady, W.; Vannice, Μ·Α· et al. Further studied the vapor phase hydrogenation of acetic acid by a series of supported platinum-iron catalysts, see J. Catal' 2002, 209, pp. 87-98. Vannice, Μ_Α·, J. Catal, 2000, 192, 322-334. Various related publications on the hydrogenation of unsaturated aldehyde selectivity are: Djerb〇ua, F; Benachour, Ό.; Touroude, R. et al., Applied Catalvsis.r Application Catalysis Period A: Introduction, 2005 '282 , pages 123-133; Liberkova, K.; Tourounde, R. et al., Mol. CataU^, et al., 2002, 180, pp. 221-230; Rodrigues, EL; Bueno, JMC et al., Applied Catalysis A: Introduction, 2004, 257, pp. 210-211; Ammari, F.; Lamotte, J.; Touroude, R. et al., Applied Catnly^Q, 2004, 221 '32-42; Ammari , F.; Milone, C.; Touroude, R. et al., j. Cata Bu 2005, 235, 1 -9 pages; Consonni, M.; Jokic, D.; Murzin, D. Υ·; Touroude, R., LM, 1999, 188, 165-175; Nitta, Y., Ueno, K.,, lmanaka, T. et al., Applied Catal., 1989, 56, 9-22. The method for the selective hydrogenation of crotonaldehyde to unsaturated alcohols by using a catalyst containing diamond, noodles and tin can be found in R. Touroude et al.: Djerbc) ua, F; Benachour, D.; Touroude , R. et al., Applied Catalysis A: Introduction, 2〇〇5, 282, 123-133; and Liberkova, K.; Tourounde, i?· et al., Applied Catalysis, 20〇2, 180 Period, pages 221-230; and K. Lazar et al., 201121651

Rhodes, W. D. ； Borbath, I. ； Hegedues, M. ； Margitfalvi, 1. L.^^) > Hvperfine Interactions HvDerfine Interactions(趙痛細概 SJ午用、，2002 年， 1391140 期，87-96 頁。 Μ· Santiago 等氏（Santiago, Μ· Α· Ν·; Sanchez-Castillo, Μ· A.; Cortright， R. D. ; Dumesic，1. A.等氏，J. Catal，2000 年，193 期，16-28 頁）探討 微量測熱，紅外光譜，反應動力學測量，結合量子化學計算。 在醋酸氫化t也有報導雜相系統的銖及釕之催化活性。 M A. /Minachev, Κ· M. /Buiychev, B. M. ;Ishchenko, V· Μ 等氏，Bull. AcnH 科學院公報)，USSR 1988年，2436至2439頁）。 尺tocw等氏之美國專利第5，149,680號描述利用鉑族金屬合金觸媒，催 化羧酸及其酸酐進行氫化變成醇類和/或酯的製程。尺等氏之美國專 利第4,777,303號介紹羧酸進行氫化生產醇的製程。尺治⑽等氏之美國 專利第4,804,791號描述羧酸氫化生產醇的另一製程。另見美國專利第 5,〇61，671號；美國專利第4,990,655號；美國專利第4,985,572號；和 美國專利第4,826,795號。Rhodes, WD; Borbath, I.; Hegedues, M.; Margitfalvi, 1. L.^^) > Hvperfine Interactions HvDerfine Interactions, SJ, No., 2002, 1391140, pp. 87-96. Μ· Santiago et al. (Santiago, Μ·Α·Ν·; Sanchez-Castillo, Μ·A.; Cortright, RD; Dumesic, 1. A. et al., J. Catal, 2000, 193, 16-28 Page) Explore microcalorimetry, infrared spectroscopy, reaction kinetics measurement, combined with quantum chemical calculations. Catalytic activity of ruthenium and osmium in heterogeneous systems has also been reported in hydrogenation of acetic acid. M A. /Minachev, Κ· M. /Buiychev , BM; Ishchenko, V. Μ et al., Bull. AcnH Academy of Sciences Bulletin, USSR 1988, pp. 2436-2439). U.S. Patent No. 5,149,680 to the disclosure of U.S. Patent No. 5,149,680, the entire disclosure of which is incorporated herein by reference. U.S. Patent No. 4,777,303 to et al. describes the process for the hydrogenation of carboxylic acids to produce alcohol. Another process for the hydrogenation of a carboxylic acid to produce an alcohol is described in U.S. Patent No. 4,804,791. See also U.S. Patent No. 5, 〇61,671; U.S. Patent No. 4,990, 655; U.S. Patent No. 4,985, 572; and U.S. Patent No. 4,826,795.

Malinowski 專氏(Bull. Soc. Chim. 利時化學儀會公報^，1985 年， 94 (2 )期，93-5頁）討論承載於例如二氧化矽（SI〇2 )或二氧化鈦（ή〇2 ) 的支撐體物料上之雜相低價鈦對醋酸之催化反應。 雙金屬釕-錫/二氧化矽觸媒之製法係使四丁基錫和承載於二氧化矽上之 二氧化釕反應。（Loessard 等氏，Studies in Surface Science and Catnip 表鱼赴_學與催化之研塞（1兇9年），卷_日期:1988年，48期（表面反 應結構），591-600頁）。 醋歐之催化概也被研冑，彳物，Hindermann料，等氏， iChem. Res., Synopses J Chem, Res., Synopses-M.，i98〇 年，11期’ 373頁），揭露醋酸在鐵和驗促進的鐵上之催化還原。 既存製程叙各種阻礙商業化可行性關題包括：⑴麵對乙醇的選 擇率不夠；（ii) _可為昂貴和/成乙醇的珊率低和產生不合需 201121651 要的副產物·，（iii)過度的作溫度和壓力；和/或（iv)觸媒壽命不足。 因此，需要尋找新的氫化觸媒，對乙醇具有高選擇率，轉化率和產率， 且具有適合商業氫化製程之觸媒壽命。 【發明内容】 本發明提供用於醋酸氫化高選擇率形成乙醇之觸媒及製程。 在一實施方針，例如’本發明涉及—糊媒，包括第—金屬，含石夕支 撐體，至少一偏矽酸鹽支撐體改性劑’及任意之第二金屬。在另一實施 方案中’觸媒包括第-金屬’第二金屬，含碎支撑體，及至少—支標體 改性劑。第一金屬選自包含週期表IB，IIB, IIIB，IVB，VB，VIB，viffi或 viii族過渡金屬，系金屬，系金屬，或說，iva，va，或心的任 一金屬之群組。尤佳為，第—金屬可選自包含銅，鐵，鈷，鎳，釕， 姥，鈀，餓，銀’始，鈦，辞，鉻，銶，翻及鶴之群組。第二金屬選自 包含銅’鉬，錫，絡，鐵’銘，奴，鎢，把，銘，鑭，飾，猛，鍊及錄 之群組。第一金屬用量可為觸媒總重量的〇〗到25重量％。 第二金屬可選自包含銅，翻，錫，絡，鐵，钻，飢，鎢，把，翻，爛， 鈽，錳’釘’銖’金及錄之群組。第一金屬用量可為觸媒總重量的〇1 到10重夏％，第二金屬可為觸媒總重量的〇1到10重量％。一方面， 該觸媒可包括第二金屬’可選自包含鈷，把，釕，銅，辞翻，錫及鍊 之群組，和/或其用量可為觸媒總重量的0·05到4重量％。 較佳為第-金屬伽自，和第二金屬係錫，且賴錫摩爾比從⑷〇 6至 〇·6 0.4。在另-首選組合中，第一金屬係把和第二金屬係鍊’且鍊對 把摩爾比從0.7.0.3到〇_85 : 0.15。如上所述，此等觸媒適合用作觸媒， 做為氫化觸舰轉化為乙醇，和醋轉化率至少1()%。此外，觸 媒對乙醇的選擇率可能有至少8G%和/或對Μ，乙狀二氧化碳的選 擇率小於4%。在-個種實施方案中，每觸個小時的觸媒使用，其產 201121651 率跌幅小於6%。 該含石夕支撐體可以有選擇性地選自包含二氧化石夕， 二氧化石夕，高純度二氧切及其混合—物之量 ='=;:r9 編。—表：Malinowski (Bull. Soc. Chim. Liehe Chemical Society Bulletin ^, 1985, 94 (2), 93-5) discusses the bearing of, for example, cerium oxide (SI〇2) or titanium dioxide (ή〇2) The catalytic reaction of the heterogeneous titanium on the support material on acetic acid. The bimetallic bismuth-tin/cerium oxide catalyst is prepared by reacting tetrabutyltin with cerium oxide supported on cerium oxide. (Loessard et al., Studies in Surface Science and Catnip, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 9 years, _ date: 1988, 48 (surface reaction structure), 591-600 pages). The catalysis of vinegar and euro is also studied, sputum, Hindermann, et al, iChem. Res., Synopses J Chem, Res., Synopses-M., i98 Leap Year, 11 issue [373 pages), revealing acetic acid in Iron and test promote the catalytic reduction of iron. The existing process of imposing various commercial barriers to commercialization include: (1) insufficient selection rate for ethanol; (ii) _ can be expensive and / / ethanol into the low rate and produce undesirable by-products 201121651 ·, (iii Excessive temperature and pressure; and / or (iv) insufficient catalyst life. Therefore, there is a need to find new hydrogenation catalysts with high selectivity, conversion and yield for ethanol, and a catalyst life suitable for commercial hydrogenation processes. SUMMARY OF THE INVENTION The present invention provides a catalyst and process for the formation of ethanol with high selectivity for hydrogenation of acetic acid. In one embodiment, for example, the present invention relates to a paste medium comprising a first metal, a ruthenium support, at least one metasilicate support modifier, and any second metal. In another embodiment, the catalyst comprises a first metal, a second metal, a broken support, and at least a support modifier. The first metal is selected from the group consisting of transition metals of the Periodic Tables IB, IIB, IIIB, IVB, VB, VIB, viffi or viii, metals, metal, or iva, va, or any of the metals. More preferably, the first metal may be selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, osmium, palladium, hungry, silver, titanium, rhodium, chrome, ruthenium, turn and crane. The second metal is selected from the group consisting of copper 'molybdenum, tin, lanthanum, iron 'Ming, slave, tungsten, handle, Ming, 镧, 饰, 猛, chain and recorded. The amount of the first metal may be from 〇 to 25% by weight based on the total weight of the catalyst. The second metal may be selected from the group consisting of copper, turn, tin, iron, iron, diamond, hunger, tungsten, turn, turn, rotten, bismuth, manganese 'nail' The first metal may be used in an amount of from 1 to 10% by weight based on the total weight of the catalyst, and the second metal may be from 1 to 10% by weight based on the total weight of the catalyst. In one aspect, the catalyst can include a second metal 'which can be selected from the group consisting of cobalt, rhodium, ruthenium, copper, rhodium, tin, and chains, and/or the amount thereof can be from 0.05 to the total weight of the catalyst. 4% by weight. Preferably, the first metal is gamma, and the second metal is tin, and the molar ratio of lysine is from (4) 〇 6 to 〇·6 0.4. In another preferred combination, the first metal tie and the second metal tether' and the chain pair molar ratio is from 0.7.0.3 to 〇_85: 0.15. As noted above, these catalysts are suitable for use as a catalyst, converted to ethanol as a hydrogenated contact vessel, and have a vinegar conversion of at least 1%. In addition, the selectivity of the catalyst for ethanol may be at least 8 G% and/or for bismuth, and the selectivity for sigma carbon dioxide is less than 4%. In each of the various embodiments, the amount of catalyst used per hour was reduced by less than 6%. The rock-bearing support may be selectively selected from the group consisting of sulphur dioxide, sulphur dioxide, high purity dioxin and mixtures thereof = '=;: r9. -table:

Π:1 ’例如’偏矽酸鹽支撐體改性劑，可選擇性地選自包含 ω驗土金屬偏魏鹽，㈤驗金屬偏概鹽，㈤元切期表IIB ==鹽’（iv)週期表ΙΙΙΒ族_魏鼓其混合物之群組。 、；，支擇體改性劑可為金屬偏魏鹽，而該金屬選自包含 可=姐ΐ筑，紀和辞之群組，較佳為Casi03。支揮體改性劑的用量 了為觸媒總重量的G.1%至5〇重量％。 在另一實施方案中，觸媒滿足下式：Π: 1 'for example, a bismuth citrate support modifier, which can be selectively selected from the group consisting of ω soil-measuring metal salts, (5) metal-based partial salts, (5) yuan cut-off table IIB == salt' (iv The periodic table ΙΙΙΒ _ _ _ drum group of the mixture. The modified body modifier may be a metal meta-salt salt, and the metal is selected from the group consisting of: ΐΐ筑, 纪和辞, preferably Casi03. The extender modifier is used in an amount of from G. 1% to 5% by weight based on the total weight of the catalyst. In another embodiment, the catalyst satisfies the following formula:

PtvPdwRexSnyCapSiqO,, =中：⑴V : y的比例在3 : 2和2 : 3之間，和/或（π) w : X的比例 矛1 . 5之間;和挑選p和q使得p : q是從i : 2〇到丄：2⑻與 挑選Γ值’以滿足價態要求’及挑選v和w使得： 0.005 < (3·2—-+1·75νν) < 0.05. q 作為另-選擇可滿足下式：PtvPdwRexSnyCapSiqO,, = Medium: (1)V: The ratio of y is between 3:2 and 2:3, and / or (π) w: the ratio of X to Spike 1.5; and picking p and q such that p: q is From i : 2〇 to 丄: 2(8) and picking the Γ value 'to satisfy the valence requirement' and picking v and w such that: 0.005 < (3·2—-+1·75νν) < 0.05. q as another-option Can satisfy the following formula:

PtvPdwRexSnyAlzCapSiqOr， 其中·（1) V和y的比例是在3 : 2和2 : 3之間，及/或（ϋ) w和χ的 比例在1 · 3和1 : 5之間，而控制ρ及ζ，和鋁和鈣原子的相對位置使 得其表面的布朗斯特酸基，，（Bmnsted acid sites)被支樓體改性劑平衡； 和選定P及^是使得p : q的比例是從1 : 20到1 : 200與選定r值，以 滿足價㊣要求’贿v和w使得： 6 201121651 〇.005<-^^LLZ5m〇<〇〇5 <1 - · · 除了觸媒，本發明還涉及該觸媒之製法。一優選的實施方案涉及—種 媒的製法，製程的步驟包括（a)歧第—金屬前體接觸改質含石夕支^ 體，形成浸潰支撐體，其中改質後的含矽支撐體包括含矽材料Z至少: 個種偏魏鹽支樓體改性劑;及（b)在能有效還原第—金屬而形成二觸 媒的條件下，加熱浸潰的支撐體。較佳為，在至少部分還原氣氛下加熱。 或者，該製程可能會進一步包括步驟（c)使至少一偏矽酸鹽支撐體、改 性劑或其前體接觸含矽材料，形成改性支撐體前體；和（d)在能有吱 形成改性支撐體的條件下，加熱改性支撐體前體，還可進一步煅燒觸 媒。-方面’無論是在步驟（a)和（b)之前，之後或同時，這個製程 還包括浸潰和還原第二金屬碰，在支碰上產丨不同於第―金屬的第 —金屬之步驟。在另一方面，無論是在步驟（a)和之前，之後或 同時’這個t㈣包括浸潰和還原第三金屬前體，在支標體上產出不3同 於第一金屬和第二金屬之第三金屬的步驟。 此外，本發明另-實施方案涉及-製程包括（a)使第_麵前體接觸 改質之含碎支#體，該支雜包括至少—種支撐體改性劑，其_第一金 屬選自包含銅，鐵，钻，錄，釕，錢，，餓，銀，，鈦'，辞，絡， 鍊，紐狀群組；⑻使不同於第—金屬之第二金屬前體接觸到改質 3石夕支撐體，其中第二金屬選自包含銅，翻，錫，鉻，鐵，m 把’始’鋼’鈽’猛’銖及鎳之群組；和⑷在能有效還原第一金屬 和第二金屬祕成金屬觸賴條件下，加献質之切續體。一方 面，加熱是發生在步驟⑴和（b)之後。另夕卜，在步驟⑷和㈦ .之間加熱（至少部分可選擇性地發生在還原氣氛τ)還原第一個種金 屬’和在步驟（a)及㈦之魏原第二金屬。或者，製程可進一步包 括步驟（〇使至少有-财Μ讀财性戦其碰賴切及材 201121651 料，形成改質支撐體前體；和（d)在能有效形成改質支撐體條件下加 熱改質支標體前體，還可進一步煅燒觸媒。該煅燒可在步驟（a)和 之後或步驟（a)及（b)之間進行。在另一方面，在與步驟（a)和（b) 之前、之後或同時，製程進一步包括浸潰和還原第三金屬前體成為不同 於第一金屬和第二金屬的第三金屬，承載於支撐體上。 就本發明製程而言，用於本發明製程的觸媒及其成分，例如，第—金屬， 第二金屬，第三金屬（可選擇性地），（含矽)支撐體，和（偏矽酸鹽）支 撐體改性劑’可作為上述有關本發明的觸媒。 【發明說明】 本發明涉及用於使醋酸氫化生產乙醇的觸媒。所採用的觸媒包括至少一 種金屬，細支#體，及至少-種支改性劑，較佳為偏魏鹽^稽 體改性劑。本發明還涉及到製備這些觸媒之流程。 牙 醋酸氫化形成乙醇可醋酸氫化形成乙醇可由以下反應式表示. 0 2H2PtvPdwRexSnyAlzCapSiqOr, where ·(1) the ratio of V and y is between 3:2 and 2:3, and/or the ratio of (ϋ) w and χ is between 1 · 3 and 1: 5, and the control ρ and ζ, and the relative positions of the aluminum and calcium atoms such that the surface of the Brnsted acid sites, (Bmnsted acid sites) are balanced by the building bulk modifier; and the selected P and ^ are such that the ratio of p: q is from 1 : 20 to 1: 200 with the selected r value to meet the price requirement [Brit v and w make: 6 201121651 〇.005<-^^LLZ5m〇<〇〇5 <1 - · · In addition to the catalyst, this The invention also relates to a method of making the catalyst. A preferred embodiment relates to a process for preparing a medium, the process comprising the steps of: (a) dissimilaring a metal precursor contacting a modified yttrium support to form an impregnation support, wherein the modified ruthenium support The invention comprises at least: a bismuth-containing material Z: at least: a partial Wei-salt branch modifier; and (b) a heated impregnated support under conditions effective to reduce the first metal to form a two-catalyst. Preferably, the heating is carried out under at least a partial reducing atmosphere. Alternatively, the process may further comprise the step of (c) contacting at least one metasilicate support, a modifier or a precursor thereof with a ruthenium-containing material to form a modified support precursor; and (d) capable of having a ruthenium Under the condition that the modified support is formed, the modified support precursor is heated, and the catalyst can be further calcined. - Aspects - whether before, after or at the same time as in steps (a) and (b), the process further comprises the steps of impregnating and reducing the second metal bump, which is different from the first metal of the first metal. . On the other hand, whether in step (a) and before, after or at the same time 'this t (four) includes impregnation and reduction of the third metal precursor, the output on the support body is not the same as the first metal and the second metal The third metal step. In addition, another embodiment of the present invention relates to a process comprising: (a) modifying a first precursor to contact the modified body, the inclusion comprising at least one type of support modifier, wherein the first metal is selected Self-contained copper, iron, drill, record, 钌, money,, hungry, silver,, titanium ', word, network, chain, new group; (8) make the second metal precursor different from the first metal contact a 3 stone support, wherein the second metal is selected from the group consisting of copper, turn, tin, chrome, iron, m, 'starting' steel '钸' fierce' and nickel; and (4) can effectively restore the first The metal and the second metal secret metal are in contact with each other, and the cut-off body is added. On the one hand, heating occurs after steps (1) and (b). Further, between the steps (4) and (7), heating (at least partially selectively occurring in the reducing atmosphere τ) reduces the first species of metal 'and the second metal of the Wei original in steps (a) and (7). Alternatively, the process may further comprise the steps of (at least having - read the financial property, ignoring the cut material and the material 201121651 to form a modified support precursor; and (d) under conditions effective to form the modified support The catalyst can be further calcined by heating the modified precursor precursor. The calcination can be carried out between step (a) and after or between steps (a) and (b). On the other hand, in step (a) And (b) before, after or at the same time, the process further comprises impregnating and reducing the third metal precursor into a third metal different from the first metal and the second metal, carried on the support. Catalysts and compositions thereof for use in the process of the present invention, for example, a metal-, a second metal, a third metal (optionally), a (ruthenium-containing) support, and a (meta-rutate) support modification The agent ' can be used as the above-mentioned catalyst for the present invention. [Invention] The present invention relates to a catalyst for hydrogenating acetic acid to produce ethanol. The catalyst used includes at least one metal, fine support, and at least - The modifier is preferably a modified salt of a Wei salt. Invention also relates to processes for preparing these catalyst of Dental hydrocortisone acetate, hydrocortisone acetate, is formed formed ethanol may be ethanol represented by the following reaction formula. 0 2H2

意外地發現，本發明觸媒於醋酸氫化製程中提供高選擇率給乙氧基化 物’如乙醇及醋酸乙酯，特別是乙醇。本發明實施方案有益於工業應用， 可在經濟上可行的規模生產乙醇。 、 本發明觸媒包括第一金屬和可選擇性的一種或一種以上之第二金屬，第 三金屬或其他金屬，承載於讀體上。在這種情況下，用來修飾"金屬" 的序數"第-”、"第二"、”第三"等，是為了表明金屬各自不同。所有承 載的金屬總重量較佳觸媒重量的（U到25重量％，例如從〇 1到 15重量％ ’或(U重頻至Π)重量.在本說明書中，除另有註明外， 重量百分率是根據觸媒的總重量(包括金屬和支撐體)而言。在觸媒中金 屬可能存在為-種或多種金屬氧化物的形式。在測定在觸媒巾金屬重量 201121651 百/7率時，忽略結合於金屬之任何氧的重量。 第金屬可為70素週期表1Β，ΠΒ，ΠΙΒ，IVB，VB，VIB，VHB或丽族過 渡金屬’罐金屬’射系金屬或任一週期表ιπΑ，隱，Μ或佩族的 金屬。在優選的實施方針，第—金屬選自包含銅，鐵，銘，錄，釕， 錄把餓，銥，始，欽，鋅，絡，銖，飽及鶴之群組。較佳為，第一 金屬，自包含H姑，錄和釕之群組。尤佳為，第-金屬選自舶和 鈀。當第一金屬係鉑，較佳為觸媒包含低於5重量％，如3重量％或小 於1重量％的翻，由於始昂責不易取得。 如上所述，該觸媒可選雜地還包括第二金屬，其通常會作為一種促進 齊1如果存在’第—金屬較佳為選自包含銅，銦，錫，絡，鐵，銘，鈒， 鎢鈀，始’鋼，飾，猛，釕，銖，金及錄之群組。尤佳為第二金屬 選自包含銅，錫，鈷，銖及鎳之群組。更佳為，第二個選自錫及銖。 如果觸媒包括兩種或更多種的金屬，—種金屬可以作為促進劑金屬，而 其他金屬作為主要金屬。例如，以鉑/錫觸媒而言，鉑可被認為是主要 金屬而錫可被通為疋促進劑金屬。為方便起見，本說明書是指第一金 屬作為主觸媒，而第二金屬（和可選擇性的金屬）作為促進劑。但這不 應該被視為催化活性基本機制的一個種指標。 如果觸媒包括兩種或更多種的金屬，例如第一和第二金屬，則第一金屬 用量可從0.1至10重量％ ’例如從(U到5重量％，或從〇」到3重量 %。第二金屬較佳的用量從0.1到2〇重量％，例如從〇]到10重量％， 或者從0_1到5重量％ 〇對於含兩種或兩種以上金屬的觸媒而言，兩種 或更夕種的金屬可能疋互相的合金或可包括非合金之金屬溶液或混合物。 較佳金屬比例可能略有不同，取決於使用在觸媒中的金屬種類。在一些 實施方案中，第一金屬對第二金屬的摩爾比較佳為1〇 :丨到丨：1〇，例 如，4:1 到 1:4,2:1 到 1:2，1.5:1到1:1.5，或11:1到1:1卜 現在竟然意外地發現’在醋酸形成乙醇製程中，就鉑/錫觸媒而言，為 201121651 高選擇率、轉化率和產率， 〇.4，如第Μ，1B及1C圖所亍j的摩爾比特佳為〇.4 : 〇.6至0.6 : 一步改善對乙醇的選擇率。如本文所述，藉由改性支顧，可進 就包括不同金屬的觸媒而言 媒而言，例如，在銖濃航鱗之^可^首選。就聰觸 擇率。如第2A，2B和2C _ _更:之條件下，可實現更高的乙醇選 ^ 7 jit '不’就選擇率’轉化率和產率而士，& (3 ： 1) 〇 A-Λ, , , . .3 到 0.85 . 0·15 ’ 或約 0.75 : 〇·25 擇率。％添加本靖述改質切體，可進—步改善對乙醇的選 =包=金屬之實施方案中，第三金屬可以選自蝴 第三金屬可選自上面第-或第二金屬所列的 面，第：金屬曰同於第—和第二的金屬之如即可。在較佳方 佳包含钻’把，釘’銅，辞，始，錫及銖之群組。尤 ψ1~選自姑’把及釕。如果存在，第三金屬總重量在0.05和4 以’例如’ 0.1到3重量％ ’或〇Λ到2重量％。 案中金屬觸媒包括第一金屬，沒有額外的金屬（第二金屬 在此貫施方案中，第一金屬較佳用量為0.1至10重量％。在另— 個實化方案巾’觸媒包含兩種或賴以上的金屬承載於支雜上。表1 2出本發明實施方案各種觸翻較佳具體金屬組合。若金屬觸媒包括第 金屬和第二金屬，則第-金屬用量較佳為0.1到5重量％，而第二金 $用量較佳為G.1到5重量％。金屬觸媒包括第―，第二和第三金屬， 2第-金屬用量較佳為Q1到5重量％，第二金屬用量較佳 0弟二金屬用量較佳為0.1到2重量％。在一實施例中，第—金 =疋麵’其用量0·1到5重量％，第二金屬用量〇.1到5重量％，而第 一金屬，如杲存在，用量較佳為〇 〇5至2重量％。 201121651 屬I金 銅銅銅銅銅鎳鎳鎳鎳鈀鈀鈀鈀鈀鈀鈀鈀鈀鈀鈀鉑鉑鉑鉑鉑鉑鉑鉑鉑鉑铑铑釕釕釕釕釕釕釕釕 u u u u u^.^^^dddddddddddtHH^ Η Η η^ηη-η^μμ μ μ μ μ μ μ μ μ CCCCCNNNNPPPPPPPPPPPPPPPPPPPPP^^R'R'R'R'RRRR1 表1 觸媒金屬組合例 第二金屬 Ag銀 Cr鉻 V釩 W鎢 Zn辞 Au金 Re銖 V釩 W鎢 Co錄 Cr鉻 Cu銅 Fe鐵 La鑭 Mo鉬 Ni鎳 Re銖 Sn錫 V釩 W鎢 Co姑 Cr鉻 Cu銅 Fe鐵 Mo鉬 Sn錫 Sn錫 Sn錫 Sn錫 Sn錫 Cu銅 Ni鎳 Co钻 Cr鉻 Cu銅 Fe鐵 La鑭 Mo銦 Ni鎳 Sn錫 第三金屬Surprisingly, it has been found that the catalyst of the present invention provides a high selectivity to the ethoxylates such as ethanol and ethyl acetate, particularly ethanol, in the acetic acid hydrogenation process. Embodiments of the present invention are beneficial for industrial applications and can be produced on an economically viable scale. The catalyst of the present invention comprises a first metal and optionally one or more second metals, a third metal or other metal, carried on the read body. In this case, the ordinals used to modify "metal""--,"second","third", etc., are meant to indicate that the metals are different. The total weight of all supported metals is preferably from the weight of the catalyst (U to 25% by weight, for example from 〇1 to 15% by weight' or (U to frequency to Π) weight. In this specification, unless otherwise stated, the weight The percentage is based on the total weight of the catalyst (including metal and support). The metal may be in the form of one or more metal oxides in the catalyst. When measuring the metal weight of the catalyst towel 201121651 100/7 rate Ignore the weight of any oxygen bound to the metal. The metal may be a 70-period periodic table, ΠΒ, ΠΙΒ, IVB, VB, VIB, VHB or Li transition metal 'can metal' shot metal or any periodic table ιπΑ , hidden, Μ or Pei metal. In the preferred implementation policy, the first metal is selected from the group consisting of copper, iron, Ming, recorded, 钌, recorded, hungry, 铱, 初, 钦, 锌, 络, 铢, 满Preferably, the first metal is self-contained with a group of H, a group, and a group of bismuth. More preferably, the first metal is selected from the group consisting of palladium and palladium. When the first metal is platinum, preferably a catalyst. The inclusion of less than 5% by weight, such as 3% by weight or less than 1% by weight, is difficult to obtain due to the initial blame. As described above, the catalyst optionally includes a second metal, which is generally used as a kind of promotion. If present, the first metal is preferably selected from the group consisting of copper, indium, tin, complex, iron, and tin. , Tungsten and Palladium, the beginning of 'steel, decoration, fierce, 钌, 铢, gold and recorded groups. Especially good for the second metal selected from the group consisting of copper, tin, cobalt, antimony and nickel. More preferably, the first Two are selected from tin and antimony. If the catalyst comprises two or more metals, the metal can act as a promoter metal and the other metals act as the main metal. For example, in the case of a platinum/tin catalyst, platinum can be used. It is considered to be the main metal and tin can be passed as the promoter metal. For convenience, this specification refers to the first metal as the main catalyst and the second metal (and optional metal) as the promoter. This should not be considered as an indicator of the basic mechanism of catalytic activity. If the catalyst comprises two or more metals, such as first and second metals, the first metal can be used in an amount from 0.1 to 10% by weight ' From (U to 5% by weight, or from 〇) to 3% by weight. The second metal is preferred The amount is from 0.1 to 2% by weight, for example from 〇] to 10% by weight, or from 0_1 to 5% by weight. For a catalyst containing two or more metals, two or more metals may be The alloys of yttrium may alternatively comprise a non-alloyed metal solution or mixture. The preferred metal ratio may vary slightly depending on the type of metal used in the catalyst. In some embodiments, the mole of the first metal to the second metal Better than 1〇: 丨到丨:1〇, for example, 4:1 to 1:4, 2:1 to 1:2, 1.5:1 to 1:1.5, or 11:1 to 1:1 now Unexpectedly found that 'in the acetic acid to form ethanol process, for platinum / tin catalyst, for 201121651 high selectivity, conversion and yield, 〇.4, such as Dijon, 1B and 1C map 亍j molar bits Jia Wei 〇.4 : 〇.6 to 0.6 : One step to improve the selectivity of ethanol. As described herein, by modifying the support, it is possible to use a catalyst comprising different metals, for example, in the case of a thicker scale. It is the choice of Cong. As in the 2A, 2B and 2C _ _ more: the higher ethanol can be achieved ^ 7 jit 'no' on the selection rate 'conversion rate and yield, and & (3: 1) 〇A- Λ, , , . .3 to 0.85 . 0·15 ' or about 0.75 : 〇·25 selectivity. % Adding this modified modified body, can further improve the choice of ethanol = package = metal in the implementation, the third metal can be selected from the third metal can be selected from the above - or the second metal listed The face, the third: the metal is the same as the first and second metal. Preferably, the group includes the drills, the nails, the copper, the rhyme, the beginning, the tin and the cymbal. You ψ 1~ is selected from Gu’s and 钌. If present, the total weight of the third metal is between 0.05 and 4, e.g., 0.1 to 3% by weight or 〇Λ to 2% by weight. The metal catalyst in the case includes the first metal and no additional metal (the second metal is preferably used in this embodiment, the first metal is preferably used in an amount of 0.1 to 10% by weight. In another embodiment, the catalyst contains Two or more metals are supported on the branch. Table 1 2 shows various combinations of specific metals in the embodiment of the present invention. If the metal catalyst includes the metal and the second metal, the amount of the first metal is preferably 0.1 to 5% by weight, and the second gold is preferably used in an amount of G.1 to 5% by weight. The metal catalyst includes the first, second and third metals, and the amount of the second metal is preferably from 1 to 5% by weight. The amount of the second metal is preferably from 0.1 to 2% by weight. In one embodiment, the first gold = the surface of the dough is used in an amount of from 0.1 to 5% by weight, and the second metal is used in an amount of 〇. 1 to 5% by weight, and the first metal, such as ruthenium, is preferably used in an amount of 〇〇5 to 2% by weight. 201121651 genus I gold copper copper copper copper copper nickel nickel nickel nickel palladium palladium palladium palladium palladium palladium palladium palladium palladium palladium Platinum platinum platinum platinum platinum platinum platinum platinum platinum rhodium uuuuu ^. μ μ μ μ μ CCCCCNNNNPPPPPPPPPPPPPPPPPPPPP^^R'R'R'R'RRRR1 Table 1 Catalyst metal combination example Second metal Ag silver Cr chromium V vanadium W tungsten Zn Au gold Re铢V vanadium W tungsten Co recording Cr chromium Cu Copper Fe Iron La镧MoMolybdenum Ni Nickel Re铢Sn Tin V Vanadium W Tungsten Co Cr Cr Cu Cu Fe Fe Mo Mo Sn Sn Sn Sn Sn Sn Sn Tin Sn Cu Cu Ni Ni Co Co Cr Cr Cu Cu Fe Fe La镧Mo indium Ni nickel Sn tin third metal

ο Cο C

ReRUpd 姑鍊釘le π 201121651 主要取決於麟是如何製造的’本發卿制金屬可时散在整個的支 樓體’包覆在支掠體的外層（似雞蛋殼）或襄飾在支稽體的表面上。 本發明觸媒除了含-種或更多的金屬外，還包括改質的支频，這意味 著支撐體巾包括支撑體材料和讀體改性劑，後者用來調節支顧材料 的酸度。例如’支材料上的酸基，如布輯特酸基，可用支樓體改 性劑調整之，有利於醋酸氫化中對乙醇的選擇率。支縣料的酸度可以 藉由減少支職料上的布_特酸基的數量_整之。支雜料也可藉 由支樓體改性繼變支翁料pKa而調整之。除非文意另有所指，表: 的酸度或餘量可藉由魏上陳酬量之，錢F Dei_y氏 編“Characterization of Heterogeneous Catalysts(雜相觸媒的特徵)，，，第三 早.測量表面的酸性(Measurement Acidity of Surfaces)，370-404 頁；馬 塞爾德克爾(MarcelDekker)公司’紐約簡年，全部在此納入參考。如 今已發現除了所用金屬前體和製備條件外，金屬支撐體的相互作用對乙 醇的選擇率可A有很強f彡響。彻彳是令人吃驚和意、外的是使用能調整支 樓體酸度的改性支龍’使支撐體的雜更少或更雜，已經證明比其 他氫化產品更有利於乙醇的形成。 -般對此領域之熟悉技藝者即可瞭解選擇支禮體材料，使得該觸媒體系 在所採用的製造乙醇條件下具有適當活性，選擇性和穩固性(r〇bust)。適 當的支撐體材料可能包括，例如，穩定的金屬氧化物為基礎的支撐體或 陶竞系支龍。較佳的支撐體包括含碎支顧，如二氧化⑦，氧化石夕/ 氧化鋁，IIA族矽酸鹽，如偏矽酸約，熱解二氧化矽，高純度二氧化矽 及其混合物。其他可用於本發明一些實施方案的支撐體，包括但不限 於’氧化鐵’氧化紹’二氧化鈦，氧化錯，氧化鎖，碳，石.墨，高表面 積石墨化炭，活性炭及其混合物。 在首選的實施方案中，支撐體包括具有低揮發性或者非揮發性之鹼性支 12 201121651 撐體改性劑。低揮發性錄歡揮雜足夠低，使得在觸的壽命中， 改性劑之酸度不改變。此種的鹼性改性劑，例如，可以選自包含：（〇 驗土金屬氧化物’（π)驗金屬氧化物，（iii)驗土金屬财酸鹽㈤ 驗金屬偏雜鹽，（v)週期表ΠΒ族金屬氧化物，（vi)週期表IIB族金 屬偏矽酸鹽，（vii)週期表11迅族金屬氧化物，（viH)週期表ιπΒ族金 屬偏石夕酸鹽，及其混合物之群組。除氧化物和偏赠料，其他類型的 改性劑包括硝酸鹽 '亞硝酸鹽、醋酸鹽和乳酸鹽亦可用於本發明實施方 案中。較佳為續體改性麵自包含L L銳，缺辞的氧 ，物和偏雜鹽’以及贿上述的齡物之群組。触為战體改性劑 疋石夕酸1¾ ’尤佳為财峡(CaSi〇3)。如私雜改彳蝴包括偏魏詞， 較佳為至少一部分的偏矽酸妈呈結晶的形式。 包括支題機和改性献質的支龍總重量較佳摘媒總重量之乃 重量％至99.9重量％，例如，從78重量％至9?重量％，或從8〇重量 %至95%重量。較佳祕供足量支#體改性劑，例如通過減少布朗 斯特酸基數量或可雕，尤佳為保證支的表面沒有布輯特酸基， 以調節酸度。在較佳的實施方案t，支禮體改性細量為觸媒總重^ 0.1重量％至50重量％，例如，從〇 2重量％至25重量％，由〇 5重量 重量％至8重量％。在較佳的實施方案中支= 體材料用量為觸媒總重量的25重量％至99重量％，例如，從重= %至97重量％，或35%重量％至95重量％。 在-讎實施方針，支碰材狀—種含較雜材料選自包含二氧 切，二氧切/氧脑，IIA族猶鹽，如偏魏約，熱解二氧化石夕， 高純度二氧切及其齡物之群纟且。在二氧化树為抑讀體的情況 下，有利於雜!g含量低，！g是—種常見的二氧化梦之污染物，較佳為 銘佔改質後支樓體總重量的i重量％以下，例如，低於〇 5重量％或们 13 201121651 p二下在w方面，較佳為‘熱解二氧化矽，，㈣r〇genicsiM，因 純度可超過99·7重魏。在整份制書中高純度二氧化石夕， t酸性污染物_，如果有的話，其含量低於〇3重量％，例如， / ” 0.2重量％或低於〇1重量％之水平。當偏石夕酸细來作為支撑體 =劑，作為支樓體材料的二氧切純度沒有必要相當嚴格，雖然铭仍 =不可取的通常^會有意添加。此種二氧切德含量，例如，可 古^於1G重量％ ’如’小於5重量％或低於重量％。在支撐體包括 f樓體3改性敝纽下，2 «魅ι« «%大量細性雜質(如 是可的’只要它們被適量支撐體改賴大幅平衡即可。 3夕支撐體材料(如—氧切)絲面積難為至少約％平方米/克 如’至少約100平方米/克，至少約15〇平方来/克，至少約2〇〇平方米/ 克或最優駐少約25〇平方米/克。就細㈣，難為切支標體材 枓(如二氧化石夕)表面積從50到_平方米/克，例如，從至平 方^/克或從1GG到3GG平方概。在· f卜高表_二氧化 石夕疋f具至少約250平方米/克表面積之二氧化石夕。在本說明書中表 面積疋指BET|l^©^，這意味雜據ASTMD6550_(〕4所測定的表 面積，全部納入於此作為參考。 該含石夕支撐體材料也較佳為平均孔概5到奈米(⑽），例如從$ 不米從5至25奈米或約5至1〇奈米’該孔徑以采式孔隙分析 儀;則疋’而平均孔隙體積為〇 5至2 〇立方厘米/克，例如，從〇 7到1 $ 立方厘槪或約0.8至U立方厘米/克，亦以汞式孔隙分析儀測定。. ^支撐體㈣的形態，從而導朗觸㈣物雜，可能有很大的不 5在二霄施方案中，支擇體材料的形態和/或觸媒的組成物的形態 ，然較佳呈圓柱顆粒，但亦可呈粒狀，擠出體，球狀，喷霧乾燥微粒， 她，五雜，三餘，四餘，多餘，或片狀。健為含發支標體 14 201121651 材料也態’能使堆積密度(packing density)為〇」至！ 〇克/立方厘米 例如，從0.2至〇·9克/立方厘米或從0.5到〇 8克/立方厘米。歡小 开而I it切錢體材概料具有平均織，例如，這意味著為球 形顆粒的餘或非球形顆粒之等效球形直徑從譲至ι 〇厘米例如， :1至G.5厘米或從〇.2至〇 4厘米。由於—種或更多種的金屬承載於 =樓體上或内，-般浸潰餘小，應該竹大⑽彡響整體觸媒顆粒 的大小。因此’上述粒徑-般都義於改性後的支撐體以及最終的 顆粒。 邮 ，佳的二氧切支撐體材料是卿138高表面（職）的二氧化石夕觸媒 載體(Samt-Gobain NorPro公司）。此SS6U38二氧化石夕包含㈣重旦 面積二氧化石夕；表面積約25Q平方米/克；以汞式孔隙分析= 2付中位孔徑約12奈米，平均孔隙體積約1〇立方厘米/克；而堆積 岔度約0.352公克/立方厘米（22镑/立方呎）。 較佳的氧化石夕/氧化紹支撑體材料是^ _ 16〇二氧化石夕（_公 =)’具有標稱直㈣5縣，密度約㈣2桃升，吸收度約〇如 克支碰’表面_ 16〇至175平方桃，和孔隨積約_毫 升/克。 ^要求觸高選醉生紅醇之實财案中，如上所述’藉由加入支樓 體改性劑，控制支題材料的布朗斯特酸性可以是相當有利的。一種可 能的醋酸氫偏產品是醋酸⑽。根據本發明，錄為支碰包括支樓 體改性劑’可以有效地抑制醋酸乙醋的生產，使觸媒組成物呈現高乙醇 的選擇率。因此’觸媒組成物較佳為具有醋酸轉換醋酸乙自旨的低選擇率 和對極不可取品(如舰)的低選擇率。較佳為控敝舰的酸度， 使得不到4%，尤佳為小於2%，最佳為小於1%的醋酸轉換為甲烧， 乙炫和二氧化碳。此外，如上所述藉由使用熱解二氧化石夕或高純度二氧 2〇Π2ΐ651 化石夕’可控制支撐體的酸度。 2實施方案中，改質後的支聰包括支賴材料和作為支撐體改性劑 、矽酸詞，其用量能有效地平衡布朗斯特酸基(例如，從二氧化石夕中 殘留的氧錄產生）。較佳為’偏魏细量為觸_重量的丨重量％ 至10重量％ ’以確保支撐體基本上是呈中性的紐性。 0 作為支撐體改性劑，例如，偏猶㉝，其表面積均可能低於支樓體材料 (如含梦支碰㈣)之表面積，在—實施㈣中，支舰材料包括含石夕 支樓體材料，為了抵消包括支撐體改性劑之效果，其中包括至少抑重 量％，例如，至少約85重量％或至少9Q重量％之高表面積二氧化石夕。 在另一方面，觸媒組成物可用下式表示：ReRUpd 姑 chain nails le π 201121651 mainly depends on how the lining is made. 'The hair of the hair of the hair can be scattered throughout the entire body of the slab body' wrapped in the outer layer of the plucking body (like an egg shell) or 襄 在 支on the surface. The catalyst of the present invention includes, in addition to the metal or more, a modified frequency, which means that the support body comprises a support material and a read modifier which serves to adjust the acidity of the material. For example, the acid group on the support material, such as the buckwheat acid group, can be adjusted with a building block modifier to facilitate the selectivity of ethanol in the hydrogenation of acetic acid. The acidity of the branch material can be reduced by reducing the amount of cloth-specific acid groups on the support material. The miscellaneous materials can also be adjusted by modifying the pKa of the branch body. Unless the context otherwise dictates, the acidity or margin of the table: can be compensated by Wei Shangchen, the money F Dei_y's "Characterization of Heterogeneous Catalysts",, the third early. Measuring Acidity of Surfaces, pages 370-404; Marcel Dekker's New York Jane, all incorporated by reference. It has now been found that in addition to the metal precursors and preparation conditions used, metals The interaction between the support and the selectivity of ethanol can be very strong. A thoroughness is surprising and intentional, and the use of modified dragons that can adjust the acidity of the building body to make the support Less or more miscellaneous, it has been shown to be more conducive to the formation of ethanol than other hydrogenated products. - Those skilled in the art will be able to understand the choice of the material to make the contact medium have the conditions for the manufacture of ethanol. Proper activity, selectivity and robustness. Suitable support materials may include, for example, a stable metal oxide-based support or a terracotta branch. Preferred supports include broken branches. Such as dioxide 7, oxidized oxide / alumina, IIA bismuth, such as abietic acid, pyrogenic cerium oxide, high purity cerium oxide and mixtures thereof. Other supports useful in some embodiments of the invention Body, including but not limited to 'iron oxide' oxides, titanium dioxide, oxidation, oxidation, carbon, stone, high surface area graphitized carbon, activated carbon and mixtures thereof. In a preferred embodiment, the support comprises a low Volatile or non-volatile alkaline branch 12 201121651 Support modifier. Low volatility is low enough that the acidity of the modifier does not change during the life of the touch. The agent, for example, may be selected from the group consisting of: (〇 soil metal oxides (π) metal oxides, (iii) soil metal salts (5) metal salts, (v) periodic oxidation of lanthanum metals (vi) Periodic Group IIB metal bismuth citrate, (vii) Periodic Table 11 Swift Metal Oxide, (viH) Periodic Table ιπ steroid metal bismuth salt, and mixtures thereof. And partial gifts, other types of modifiers Nitrate 'nitrite, acetate and lactate can also be used in embodiments of the invention. It is preferred that the modified surface be self-contained from LL sharp, missing oxygen, and hetero-salt' and bribe above A group of inferior objects. Touched as a war modifier, 疋石夕酸 13⁄4 '尤佳为财峡 (CaSi〇3). If the 杂 彳 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括The mother is in the form of crystals. The total weight of the dragon including the topic machine and the modified supplier is preferably from wt% to 99.9% by weight, for example, from 78% by weight to 9% by weight, or from 8 〇% by weight to 95% by weight. It is better to supply sufficient amount of body modifier, for example, by reducing the amount of Bronsted acid groups or can be carved, especially to ensure that the surface of the support has no cloth acid group to adjust acidity. In a preferred embodiment t, the trimming agent has a modified amount of the total weight of the catalyst of from 0.1% by weight to 50% by weight, for example, from 〇2% by weight to 25% by weight, from 〇5重量% to 8重量% %. In a preferred embodiment, the amount of the support material is from 25% by weight to 99% by weight based on the total weight of the catalyst, for example, from weight = % to 97% by weight, or from 35% by weight to 95% by weight. In the implementation of the guidelines, the material is mixed with a variety of materials selected from the group consisting of dioxin, dioxin / oxygen brain, IIA salt, such as Wei Wei, pyrolysis of sulphur dioxide, high purity two Oxygen cuts and their age groups are mixed. In the case where the dioxide tree is an inhibitor, it is advantageous for low content of mis! g! g is a common contaminant of dioxide dioxide, preferably less than i% by weight of the total weight of the branch after the modification, for example, less than 〇5 wt% or 13 201121651 p two in terms of w Preferably, it is 'pyrolysis of cerium oxide, (4) r〇genicsiM, because the purity can exceed 99. 7 Wei. In the entire book, high-purity dioxide, at the same time, t acidic contaminant _, if any, its content is less than 〇 3% by weight, for example, / 0.02% by weight or less than 〇 1% by weight. As the support body = agent, the purity of the dioxygen cut as the material of the branch body is not necessarily strict, although the name is still not desirable, it is usually intentionally added. Such a content of dioxet, for example, Can be used in 1G% by weight, such as 'less than 5% by weight or less than % by weight. In the support body including f building 3 modified 敝 New Zealand, 2 «Magic « «% of fine impurities (if it is ok) As long as they are balanced by a moderate amount of support, the area of the support material (such as - oxygen cut) is difficult to at least about % square meters / gram such as 'at least about 100 square meters / gram, at least about 15 square feet. / gram, at least about 2 square meters / gram or optimal station less than about 25 square meters / gram. On the fine (four), difficult to cut the standard body 枓 (such as dioxide dioxide) surface area from 50 to _ square meters / gram, for example, from square to ^ / gram or from 1 GG to 3 GG square. In the · f 卜 高表 _ dioxide 疋 疋 疋 with at least about 250 Square meter / gram surface area of the dioxide. In the present specification, the surface area refers to BET|l^©^, which means the surface area measured by ASTM D6550_(4), which is hereby incorporated by reference in its entirety. The bulk material is also preferably an average pore size of 5 to nanometers ((10)), for example from $5 to 25 nanometers or from about 5 to 1 nanometer 'the pore size of the pore-type analyzer; The average pore volume is 〇5 to 2 〇 cubic centimeters per gram, for example, from 〇7 to 1 $ cubic centistoke or about 0.8 to U cubic centimeters/gram, also measured by a mercury pore analyzer. ^ Support (4) Morphology, which leads to the touch (4) impurity, may have a large non-5 in the two schemes, the shape of the bulk material and / or the composition of the catalyst composition, but preferably cylindrical particles, but also It can be granulated, extruded, spherical, spray-dried particles, she, five miscellaneous, three or more, four or more, superfluous, or flaky. Jianwei contains hairpins 14 201121651 Material also can 'can pile up The packing density is 〇" to! 〇g/cm3, for example, from 0.2 to 〇·9 g/cm 3 or from 0.5 to 克 8 g / Square centimeter. Huan Xiaokai and I it cut material body material has average weave, for example, this means that the equivalent spherical diameter of the remaining or non-spherical particles of spherical particles is from 譲 to ι 〇 cm, for example, :1 to G .5 cm or from 〇.2 to 〇4 cm. Since one or more kinds of metals are carried on or within the building, the general immersion is small, and the size of the overall catalyst particles should be smashed. Therefore, the above-mentioned particle size is generally determined by the modified support and the final particles. The good dioxy-cut support material is a 138 high-surface (s) dioxide dioxide catalyst carrier (Samt). -Gobain NorPro). The SS6U38 dioxide dioxide contains (iv) heavy denier area of sulphur dioxide eve; surface area of about 25Q square meters / gram; with mercury pore analysis = 2 to pay a median pore size of about 12 nm, the average pore volume of about 1 〇 cubic centimeters / gram And the accumulation twist is about 0.352 grams / cubic centimeter (22 pounds / cubic foot). The preferred oxide oxide/oxidation support material is ^ _ 16 〇 〇 夕 _ _ _ _ _ _ _ _ _ _ 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 表面 表面 表面 表面_ 16 〇 to 175 square peaches, and the hole with the product about _ ml / gram. ^ In the actual case of demanding high-concentration of drunken red alcohol, as described above, by adding a branch modifier, it is quite advantageous to control the Bronsted acidity of the material. One possible hydrogen acetate partial product is acetic acid (10). According to the present invention, the recording of the support including the branch modifier "effectively inhibits the production of ethyl acetate, and the catalyst composition exhibits a high ethanol selectivity. Therefore, the catalyst composition preferably has a low selectivity of acetic acid conversion of acetic acid and a low selectivity to highly undesirable products such as ships. Preferably, the acidity of the control ship is less than 4%, particularly preferably less than 2%, and preferably less than 1% of the acetic acid is converted to methyl, chitosan and carbon dioxide. Further, the acidity of the support can be controlled by using pyrogenic dioxide or high-purity dioxin 2 651 fossil as described above. In the embodiment, the modified Biancong includes a support material and a support modifier, a bismuth word, which is effective in balancing the Bronsted acid group (for example, oxygen remaining from the day of the dioxide) Recorded). Preferably, the amount of 偏 为 为 至 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量0 as a support modifier, for example, the partial surface area of 33, the surface area may be lower than the surface area of the building body material (such as containing the touch (4)). In the implementation (4), the ship material includes the Shixi branch. The bulk material, in order to counteract the effect of including the support modifier, includes at least % by weight, for example, at least about 85% by weight or at least 9Q% by weight of high surface area dioxide. In another aspect, the catalyst composition can be represented by the following formula:

PtvPd^SnyCapSiqO,.,PtvPd^SnyCapSiqO,.,

式中例在3:2和2:3之間，及/或〇〇〜：乂比例在1: 3和i : 5之間。，在這個實施讀中，觸媒可包括⑴姊錫，⑻ 鈀和銖；或（iii)鉑，錫’飽和銖 較佳為選擇p和q，使得p : q是從 1 : 20到1 : 200，與選擇r值，以滿足價態要求，並選擇v和w，使Z 0.005 < (3.25v+1.75w) <〇〇5 q · 在這方面，較佳為選擇製法條件和V,叫yg和Γ值，使得至少7〇 % ’例如’至少80%或至少90%的醋酸’轉換為選自包含乙醇和醋酸 乙酯之群組，而少於4%的醋酸轉化為烷烴。尤佳為選擇製法條件和”,你 Λ：, yp, g及r值，使得至少70%，例如，至少有8〇%或至少9〇%的醋酸 轉換為乙醇’而少於4%的醋酸轉化為烷烴。在許多本發明的實施^案 中，鑑於任何細微雜質之存在，選擇p以保證支撐體的表面基本上是無 布朗斯特酸基。 、 201121651 在另—方面，觸媒組成物包括：In the formula, the ratio is between 3:2 and 2:3, and/or 〇〇~:乂 is between 1:3 and i:5. In this implementation read, the catalyst may include (1) antimony tin, (8) palladium and rhodium; or (iii) platinum, tin 'saturated 铢 preferably selected p and q such that p: q is from 1:20 to 1: 200, and select r value to meet the valence state requirement, and select v and w, so that Z 0.005 < (3.25v + 1.75w) < 〇〇 5 q · In this respect, it is preferred to select the manufacturing conditions and V , yg and enthalpy, such that at least 7 〇 % 'eg 'at least 80% or at least 90% of acetic acid' is converted to a group selected from the group consisting of ethanol and ethyl acetate, and less than 4% of the acetic acid is converted to an alkane. Especially for selecting the conditions and ", you Λ:, yp, g and r values, so that at least 70%, for example, at least 8% or at least 9% of acetic acid is converted to ethanol' and less than 4% acetic acid Conversion to Alkanes. In many embodiments of the present invention, p is selected to ensure that the surface of the support is substantially free of Bronsted acid groups in view of the presence of any fine impurities. 201121651 In another aspect, the catalyst composition include:

PtvpdwRexSnyAl2CapSiq〇r, 式中.（1) V:y比例在3:2和2 門 〇 < , . r J <間’及/或（11) w : X比例在1 : 盆表祕ΐ間。較佳為控制P及2，和師子的相對位置，使得在 ^面的布朗斯特酸基被支揮體改性劑㈣石夕轉平衡，選擇P和q w得q從1 . 2G至1 . 2G，與選擇r值，以滿足價態要求，選擇V和 =佳為，在這方面，觸媒的表面積至少i⑻平絲/克例如，至少約 平方崎，至少約·平方米/克或最佳為至少約·平方米/克； ^選擇Z和龄。在許多本發_實施转舰任何細微雜質之存在， I擇P也保祖支魏的表面實質上不含雜布朗斯特酸基，該酸基似乎 方便乙醇轉域⑽。，如上實施方該述，較佳為選擇製法 條件和⑼〇 μ及r值，使得至少的醋酸例如至少有肋 %或至少90%的醋酸，轉換為乙醇，而少於伙的醋酸轉化為烧煙。 因此’不被理論約束’在本發_媒之改性和敎氧化物支碰材料 中三加入非揮發性支碰改性劑的制如下：對抗支碰表面酸基或熱 ^定表面的效果’有可能實麟乙醇選料的所欲改善，延長觸媒的壽 命’或兩者兼而有之。-般來說，最穩定價態的氧化物支律體改性劑有 低蒸氣壓，從而有相當低揮發性或較不易揮發。因此，較佳為提供足夠 支樓體改性劑，使得：⑴抵消支碰材料表面上的酸基；㈤在氮化 的溫度下賦予抗形狀變化性，或（iii)兩者絲有之，果沒有被理論 約束’賦予抗形狀的變化性，是指賦予對抗燒結，晶粒長大，3曰0界遷移， 缺陷的遷移和位錯(dislocations)，塑性變形和/或對抗其他溫度變化引起 201121651 的微觀結構變化。 本發明的觸職微粒觸媒，在這個意義上，它不是類似汽車觸媒和柴油 油煙_設備’在塗層履中浸潰單片支碰；本發明的觸媒形成顆粒， 有時也被齡料或小獅L，呈各獅狀，而在反應胃狀大量這些形 狀觸媒於疋在反應區中提供催化金屬。通常遇到的形狀包括可選擇性 之截面之擠出體’而造喊通常先擠出呈平行__體。如上所述， 任何方便的雌職，包括球狀，喷霧乾驗雜，環狀，五邊狀和多 葉狀粒都可以使用，但較佳為圓柱形顆粒況下，形狀的選擇以 經驗為基礎，靠著感知能力使觸媒有效地接觸氣相。 f發明觸媒的—個優點是催化生產乙醇之穩定性或活性。因此，可以讚 賞的是本發明的觸媒是完全能夠被用於商業規模的醋酸氮化之工業應 用，特別是在生產乙醇。制是’它是有可能實現這_穩定性，使每 100小時的觸媒使用，觸媒的產率活性下降率低於6%，例如，每⑽ 小時不到3%或每1〇〇小時低於娜。較佳為在觸媒已達到穩定狀態 的條件後，測定一次產率活性下降率。 在-實施方針’當觸支包括高純度二氧切，且以偏魏約作 為支樓體改性劑，則在醋酸蒸氣存在，於12代至3實的溫度，空間 速度(space velocities)大於2500/小時之商業上可行的運作條件下，觸媒 的活性可以延長或穩定’觸媒的的產率和選擇率可擴展到超過一個星 期，兩個多星期，甚至幾個月。 本發明觸媒組合物較佳為改性支撐體浸潰金屬而得，但其他製程，如化 學氣相沉積也可使用。金屬浸潰前，它通常是需要形成改性支禮體，例 如’藉由支類材舰潰續财㈣而形狀。也可錢支獅改性 劑的前體’如醋酸鹽在-方面，支獅改性劑，例如，㈤吨， 添加到支龍㈣，例如，二氧切。例如，切斷,_水相懸浮液 201121651 了在去離子）C巾加人支撐體改性劑而形成，其次是加人勝體支撐體材 料。授拌由此產生的混合物，並添加辦的域體㈣，例如利用初濕 技術(Incipient wetness techniques)，在支撐體材料中加入支撐體改性劑， 該支樓體㈣的孔随積相同於續财性劑驗之體積。藉由毛細作 用可將支撑體改_狀支碰㈣的毛财。然狀性支顧經由乾 燥和般燒可雜趕支撑體改性齡液巾之水分和任何紐性成分，並將 支撐體改性劑沈積在支撐體材料上。乾燥，例如，可發生在5(rc至 300°C ’例如，從10此至20(rc，或約12(rc之溫度，可選擇性地經過 一段時間’從1到24小時，例如’從3至15小時，或6至12小時。 一旦形成後，改性支撐體可塑造成具有理想粒徑分佈的粒子，例如，平 均粒徑在0.2至0.4厘米之範圍。支撐體可擠壓，造粒，製錠片，壓搾， 粉碎或筛選到所需的粒徑分佈。任何已知的塑造支撐體材料成為所需粒 徑分佈的方法均可以採用。成形之改性支撐體的煅燒可例如在25〇艽至 800°C，如，300到700。(：或約50(TC之溫度，可選擇性地經過一段時間， 從1到12小時，例如，從2至10小時’從4至8小時或約6小時左右 完成之。 在較佳製備觸媒方法中，金屬浸潰到改性支撐體上。第一金屬的前體（第 一金屬前身）較佳為用在金屬浸潰步驟中，前體例如包括第一金屬的 水溶性化合物或水分散化合物/錯合物均可用。根據不同的金屬前體， 較佳為使用溶劑，例如水，冰醋酸或有機溶劑。第二金屬也較佳為從第 二金屬的前體浸潰於改性支撐體中。如果需要，第三金屬或第三金屬前 體也可以浸潰於改性支撐體中。 浸潰時，於乾燥改性支撐體中加入(可選擇性地滴入)第—金屬前體和/ 或第二金屬前體和/或其他金屬前體，這些前體較佳為呈懸浮液或溶液^ 之形式。由此產生的混合物可再加熱以消除溶劑，例如，可選擇性地在 201121651 真空條件下加熱。織可選擇性地配㈣度供Μ統進行額外的乾燥和 锻燒，形成最後的觸媒組成物。經加熱和/或_真空，金屬前體的金 屬較佳為分解成元素（或氧化物）_式。在某些情況下，完成移除液 態載體(例如水)可能不會發生，直_觸舰人伽和，例如在操 作過程中遇到高溫才能完成雜祕載體。在崎步射，或至少在觸 媒最初使用_段巾，這種化合物會轉換成—種金屬的雜活性形 其催化活性氡化物。 第-和第二金屬（和可選擇性的其他金屬）可同步（共浸潰）或依序浸 潰改性支禮體。在同步浸潰中，第一和第二金騎體（及可選擇性之額 外金屬前體）混合在-起，並添加到改性域體，其次是乾燥和般燒， 形成最終賴媒組合物。制步浸_言，若兩猶體倾需要的溶劑 (例如，水)不相容’可能需要採用分散劑，表面活性劑或增溶劑如草 酸銨，便於分散或溶解第一和第二金屬前體。 在依序浸潰(sequential impregnation)ttl，先加入第一金屬前體於改性支 樓體，其次是乾燥，般燒，然後由此產生的物f浸潰第二金屬前體又 作乾燥和職’以形成最終_聽成物，外的金屬祕（例如，第 三金屬的先體）可與第-和/或第二金屬前體—起加人或另用單獨的第 三浸潰轉，經麟和職域之。#然，如果需要可以制依序和同 步浸潰之組合。 合適的金麟體包括，例如，金屬純物，胺溶解化之金屬氫氧化物， 金屬硝酸鹽歧鮮酸鹽。例如，適倾之籠化合物，包括氯 鋪’氣碰敍，胺溶解化之氫氧化翻，硝酸四賴，氣德，草酸麵， 顧把’石肖酸四錄纪，氣德，草酸把，氣化她和氣化誠。一般來 說，無論從經濟角度和環境方面，較佳是可溶性勒化合物之水溶液。在 -實施方案中’第-金屬前體不是金屬物，且實質上不含金屬齒化 20 201121651 物°如果沒有局限於理論’這種非（金屬齒化物）前體被認為是增加乙 醇的選擇率。特別是優先考慮的鉑前體為硝酸四銨鉑Pt(NH3)4(N〇4)2。 在一方面，“促進劑，，金屬或金屬前體先添加到改性支撐體，其次是添加 “主”或“基本”金屬或金屬的前體。當然，相反的順序的添加法也是可能 的。促進劑金屬之示範前體包括金屬齒化物，胺溶解化金屬氩氧化物， 金屬硝酸鹽或金屬草酸鹽。如上所述，在依序的實施方案中，每一浸潰 步驟後’較佳為進行乾燥和煅燒。在上述促進的雙金屬觸媒之場合中， 可用依序浸潰’先添加促進劑金屬之後，第二浸潰步驟涉及共浸潰兩種 主要金屬，例如鉑及錫。 擧例而言，承載於Si02上PtSn/CaSi03之製備包含先浸潰CaSi03到二 氧化矽，其次是共浸潰Pt(NH3)4(N04)2和Sn(AcO)2。同樣，每一個浸潰 步驟後可為乾燥和缎燒的步驟。在大多數情況下，可以使用金屬硝酸鹽 溶液進行浸潰。但是，經煅燒能釋放金屬離子的其他各種可溶性鹽類也 可使用。他浸潰用合適的可溶性金屬鹽例子包括金屬酸類，如高銖酸溶 液，金屬草酸鹽，等等。在這種產生實質上純淨乙醇之情況下，一般較 佳為避免使用鉑族金屬鹵化前體，而是使用氮胺和/或硝酸鹽的前體。 根據一本發明實施方案之醋酸氫化成乙醇製程，可使用對此領域之熟悉 技藝者所知之多種配置-固定床反應器或流化床反應器。在許多本發明 之實施方案中，可以使用”絕熱”反應器，也就是說，很少有或根本沒有 必要在反應區通入内部管道加熱或除熱。另外，可以使用具有傳熱介質 之管殼式反應器。在許多情況下，反應區可安置在一個容器或一系列的 容器，其中介入熱交換器。然而採用本發明的觸媒進行醋酸還原製程可 在絕熱反應器進行反應被認為意義重大，因為這種反應器配置成本典型 上遠遠低於資本密集之管殼式配置。 通常情況下’觸媒用於固定床反應器中，反應器例如呈拉長的管道或管 21 201121651 形狀，其中反應物通常以蒸氣的形式，傳遞或通過觸媒。如果需要的話， 可以採用其他反應器，如流化或奔放床反應器。在某些情況下，氫化觸 媒可同時配用惰性物料，如玻璃棉，以調節反應物流通過觸媒床之壓降 和反應物與觸媒顆粒的接觸時間。 氫化反應可以在液相或氣相進行。較佳為在下列情況下進行氣相反應。 反應溫度可介於125°C至350。(：，例如，從200°C至325。(：，從225。(：至 300°C左右，或從25(TC至約30〇。〇壓力範圍從1〇千帕(Kpa)至3,000 千帕（約0.1到30大氣壓），例如，從50千帕至2,300千帕，或從1〇〇 千帕至1，500千帕·»反應物饋入反應器的，，氣體每小時空間速度GHSV) 可為大於500/小時，例如，大於ι，〇〇〇/小時，大於2 5〇〇/小時，甚至大 於5,0〇〇/小時。就範圍而言，GHSV可以從50/小時至50,000/小時，例 如，從500/小時到30.000/小時’從！·〇〇〇/小時到1〇 〇〇〇 /小時，或1〇〇〇/ 小時到6,500/小時。 在本發明餘的3-方©，氮化係在足以克服麵選空間速度通過催化 床的壓降之壓力下進行，雖然沒有禁用較高的壓力，但不言而喻，在高 空間速度，例如，5,000/小時，或6,500/小時通過反應器床可能會遇到 相當大的壓降》 雖然每摩爾醋酸反應雜兩摩爾氫，生產―摩_乙醇，實際在進料流 中氫對醋酸之摩爾比可能會有所不同：約觸：丨到丨：⑽，例如，從 50 : 1到1 : 50，從20 : 1到丨：2，或從12 :丨到丨：卜最佳為氫對醋 酸之摩爾比大於4 :卜例如，大於5 : 1或大於1〇 :卜 接觸或滞留時間也有很大的不同，取決於醋酸量，觸媒，反應器，溫度 和壓力等變數。典型的接觸_細從不到1秒，至幾個小時以上，^ 使用固&床以外的觸齡統’氣相反應首選接觸時間為在至少約秒 和100秒之間，例如，從0.3至80秒或0·4至30秒。 22 201121651 性之承魏體，如=叙醋射_魏財_麵相對惰 應盗。為氣相反應運行，在系統令溫度應控制 反 的露點(deW point)。 象概度才不低於醋酸 媒和製程，可以實現良好的醋轉解和有利的 ^擇率和產率。為本發明的目的，轉化率—詞是指在進料中醋酸轉 ^匕為醋酸以外的化合物之比率。轉化率係佔進料中醋酸賴數 =不。醋酸轉化率是由氣相層析法（GC)的數據，使用下列公式計= 得之- 醋酸轉化率(％)=】〇〇*_·[-醋_酸__的_毫摩_(進料流）_[醋酸的毫摩爾數](排出流) [醋酸的毫摩爾數](進料流） ^本么明之目的’轉化率可至少1G%，例如，至少有膽至少有奶 % ’至少有5G% ’至少有6G%，至少有7桃，或至少_。雖然觸 媒具有較高_化率是可取的，如至少_或至少寫，但若對乙醇 有高選擇率’驗低的轉化村赠受。在❹情況T這當然容易理 解’通過適當的循環流或使用較大的反應器即可補償轉化率，但彌補低 選擇率則更難。 _ 選擇率係、以轉化的醋酸之摩爾百分率表示。應該認識到每一種由醋酸 轉變之化合物具_立輯料，而選醉也和轉化率無關。例如，如 果50摩爾％的醋酸轉化為乙醇，我們指乙醇的選擇率為威。乙醇的 選擇率是由IU目層析法（GC)的數據，使訂列公式計算： 乙醇選擇率(〇/〇)=丨〇〇*___ 產出乙醇的毫摩爾數(GC) 盒楚彦..出碳的毫摩爾數(GO _谁料泊中醋醢的毫摩爾斛(G<:) 23 201121651 式中“倉絶產til座的毫摩爾數(Gey，是指氣相層析法所分析所有產品中 碳的總毫摩爾數。 就本發明的目的而言，觸媒的乙氧基化物(ethoxylates)選擇率至少60 %，例如，至少70%，或至少80%。本文中所使用的術語“乙氧基”， 具體指化合物乙醇，乙醛和醋酸乙酯。較佳為乙醇的選擇率在8〇%以 上，例如，至少有85%或至少88%。在本發明實施方案中亦較佳為對 不受歡迎的產品，如甲烷，乙烷和二氧化碳有較低之選擇率。這些不受 歡迎產品的選擇率是低於4% ’如小於2%或低於1%。較佳為在氫化 過程中，；又有檢測到這些不良產品。在一些本發明實施方案中，烧煙形 成率低，通常在2%以下，往往是在1%以下，而且在許多情況下低於 0.5%的醋酸通過觸媒轉換為烷烴，而烷烴除了作為燃料外沒有多大價 值。 產率是指氫化過程中每公斤觸媒每小時所形成特定的產品(如乙醇)的克 數。在-本發明實施方案巾，產率至少每公斤觸縣小時2⑻克乙醇， 例如，至少每公斤觸媒每小時有4〇〇克乙醇或較佳為乙醇至少6〇〇克。 以範圍而言’產率較佳為是每公斤觸媒每小時2⑽到3,_克的乙醇， 例如’ 400到2,5〇〇克或600到2,〇〇〇克的乙醇。 一些本發明觸媒可以實現醋酸轉化率至少1〇%，對乙醇選擇率至少8〇 ^ ’而產率至少每公斤觸縣小時2〇〇克乙醇。本發明觸媒的一子群可 以實現醋酸轉化率至少观，對乙醇選擇率至少8()%，對不良化合物 選擇率低於4%，而產率至少每公斤觸縣小時_克乙醇。 在另-實财” ’本發明提供—種由本發明製輯形成的乙醇粗製 品。在任何後續加工(提純和分離)之前，本發明氫化製程所形成的乙醇 粗製品通常會主要包括未反應的醋酸和乙醇^在—些典型實施方案中， 乙醇粗製品包括乙醇，其含量佔乙醇粗製品總重量之15重量％至％重 24 201121651 量％ ’例如，20重量％至50重量％ ’或從25重量％至％重量％。較 佳為乙醇粗製品含有至少22重量％乙醇，至少28重量％乙醇或至少 44重量％的乙醇。乙醇粗製品通常將進—步包括未反應醋酸，視轉化 率而定’例如’含量從〇到8G重量％，例如，從5至8()重量％，從 2〇到7〇 «%，從28到7〇重魏或從Μ到&重挪。由於水是反 應製程中形成的，水也將出現於乙醇粗製品中，例如，含量從5至％ 重频，例如，從K)至3〇重量％或1〇至26重量【其他成分例如， 醋’ m贿及二氧化碳，如果檢測到，其總量可能低於ι〇 重量％，例如，小於6重量％或小於4重量％。以範圍而言，其他成分 含量從Μ到1G重频’例如，從㈣6重量％，或從至4重量 在本發明不同實施方案中，乙醇粗製品示範性組成列於下面 的表2中。 表2 乙醇粗製品之組成 成分濃度 濃度 (重量％) 濃度 (重量 遭度 (重量°/〇) 濃度 ，壬真0/、 乙醇 醋酸 水 其他 15-70 5-80 5-30 <10 15-70 20-70 5-30 <10 20-50 28-70 10-30 <6 ----- 、里董y〇) 25-50 44-65 10-26 _ <4 25 201121651 表3 乙醇粗製品之組成 組成物A 濃度(重量〇/0) 組成物B 濃度(重量％) 組成物C 濃度(重量°/〇) 17 26 45 74 53 20 7 13 25 2 8 10 乙醇 醋酸 水PtvpdwRexSnyAl2CapSiq〇r, where (1) V:y ratio is 3:2 and 2 thresholds < , . r J < between 'and/or (11) w : X ratio is 1: basin secret . Preferably, the relative positions of the P and 2, and the teacher are controlled such that the Bronsted acid group on the surface is balanced by the support modifier (4), and the P and qw are selected from 1. 2G to 1 2G, and select r value to meet the valence requirement, select V and = good, in this respect, the surface area of the catalyst is at least i (8) flat wire / gram, for example, at least about square, at least about · square / gram or The best is at least about · square meters / gram; ^ choose Z and age. In many of the present inventions, the presence of any fine impurities in the transshipment, I choose P also protects the surface of the progenitor Wei substantially free of heterobrown acid groups, which seem to facilitate ethanol transfer (10). Preferably, as described above, the process conditions and (9) 〇μ and r values are selected such that at least acetic acid, for example at least rib% or at least 90% acetic acid, is converted to ethanol, and less than the acetic acid is converted to burn. smoke. Therefore, 'not bound by theory' is added to the non-volatile support modifier in the modification of the present invention and the bismuth oxide support material as follows: the effect of resisting the acid surface or the surface of the surface of the surface 'There may be the improvement of the choice of the raw material of the ethanol, extending the life of the catalyst' or both. In general, the most stable valence oxide modifiers have a low vapor pressure and are relatively low volatility or less volatile. Therefore, it is preferred to provide a sufficient amount of the building body modifier such that: (1) counteracts the acid groups on the surface of the supporting material; (5) imparts resistance to shape variability at the temperature of nitriding, or (iii) both, If it is not theoretically constrained 'to impart resistance to shape variability, it means giving resistance to sintering, grain growth, 3曰0 boundary migration, defect migration and dislocations, plastic deformation and/or resistance to other temperature changes. 201121651 Microstructural changes. The contact particulate catalyst of the present invention, in this sense, is not similar to automotive catalysts and diesel fume _ equipment' impregnated monolithic impact in the coating track; the catalyst of the present invention forms particles, sometimes also aged The material or the lion L is in the shape of a lion, and in the reaction of the stomach, a large amount of these shape catalysts provide a catalytic metal in the reaction zone. Commonly encountered shapes include extrudates of selectively cross-sections that are typically extruded first in parallel. As mentioned above, any convenient female position, including globular, spray dry, mixed, circular, pentagonal and multilobal particles can be used, but preferably in the case of cylindrical particles, the shape is chosen to experience Based on the ability to sense, the catalyst effectively contacts the gas phase. An advantage of the invention of the catalyst is the catalytic stability or activity of the production of ethanol. Therefore, it can be appreciated that the catalyst of the present invention is fully industrially applicable to commercial scale acetic acid nitridation, particularly in the production of ethanol. The system is 'it is possible to achieve this stability, so that every 100 hours of catalyst use, the yield decline rate of the catalyst is less than 6%, for example, less than 3% per hour (1) or every hour Less than Na. Preferably, the rate of decline in yield activity is measured once the condition that the catalyst has reached a steady state. In the implementation guideline, when the contact support includes high-purity dioxygen cut, and the Weiwei is used as the building bulk modifier, the acetic acid vapor is present, and the space velocity (space velocities) is greater than the temperature of 12 to 3 Under 2500/hour of commercially viable operating conditions, the activity of the catalyst can be extended or stabilized. The yield and selectivity of the catalyst can be extended to more than one week, more than two weeks, or even several months. The catalyst composition of the present invention is preferably obtained by impregnating a metal with a modified support, but other processes such as chemical vapor deposition may also be used. Before the metal is impregnated, it usually needs to form a modified ritual body, for example, by the shape of a ship. It is also possible to use a precursor of the lion modifier, such as acetate in the aspect, a lion modifier, for example, (five) tons, added to the dragon (four), for example, dioxo. For example, the cut-off _ aqueous phase suspension 201121651 is formed by adding a support modifier to the deionized C towel, followed by the addition of the body support material. The mixture thus produced is mixed, and the domain body (4) is added, for example, by using Incipient wetness techniques, a support modifier is added to the support material, and the pore volume of the branch body (4) is the same as The volume of the renewal drug test. By means of capillary action, the support can be changed to _ shape (4). The dryness and the usual burn-up can be used to wash the moisture and any constituents of the support-modified liquid wipes and deposit the support modifier on the support material. Drying, for example, can occur at 5 (rc to 300 °C 'for example, from 10 to 20 (rc, or about 12 (temperature of rc, optionally over a period of time from 1 to 24 hours, eg 'from 3 to 15 hours, or 6 to 12 hours. Once formed, the modified support can be molded into particles having a desired particle size distribution, for example, an average particle size in the range of 0.2 to 0.4 cm. The support can be extruded, granulated. , tableting, pressing, comminuting or screening to the desired particle size distribution. Any known method of shaping the support material to the desired particle size distribution can be employed. The calcination of the shaped modified support can be, for example, 25〇艽 to 800°C, eg, 300 to 700. (: or about 50 (TC temperature, optionally over a period of time, from 1 to 12 hours, for example, from 2 to 10 hours' from 4 to 8 In a preferred method of preparing the catalyst, the metal is impregnated onto the modified support. The precursor of the first metal (the first metal precursor) is preferably used in the metal impregnation step. The precursor may include, for example, a water-soluble compound or a water-dispersible compound/compound of the first metal. Depending on the metal precursor, it is preferred to use a solvent such as water, glacial acetic acid or an organic solvent. The second metal is also preferably impregnated from the precursor of the second metal in the modified support. If necessary, The trimetallic or tertiary metal precursor may also be impregnated in the modified support. During the impregnation, the first metal precursor and/or the second metal may be added (optionally) to the dry modified support. The precursors and/or other metal precursors are preferably in the form of a suspension or solution. The resulting mixture can be reheated to eliminate the solvent, for example, optionally under vacuum in 201121651. The woven fabric can be selectively blended with (four) degrees for additional drying and calcination to form the final catalyst composition. The metal of the metal precursor is preferably decomposed into elements (or oxides) by heating and/or vacuum. In some cases, the completion of the removal of the liquid carrier (such as water) may not occur, straight-to-ship contact, such as high temperature in operation to complete the messy carrier. , or at least initially in the catalyst, using a snippet, this The compound is converted into a heteroactive form of the metal and its catalytically active telluride. The first and second metals (and optionally other metals) can be simultaneously (co-impregnated) or sequentially impregnated with modified celestial bodies. In the simultaneous impregnation, the first and second gold riding bodies (and optional additional metal precursors) are mixed in and added to the modified domain, followed by drying and burning, forming the final solvent. Composition. Step dip _, if the solvent (for example, water) required for the two scorpions is incompatible 'may need to use a dispersant, surfactant or solubilizer such as ammonium oxalate, easy to disperse or dissolve the first and the first The second metal precursor. In the sequential impregnation ttl, the first metal precursor is first added to the modified branch body, followed by drying, burning, and then the resulting material f is impregnated with the second metal. The body is used for drying and occupation to form the final _ listener, the outer metal secret (for example, the precursor of the third metal) may be added to the first and/or second metal precursor or separately. The third dipping turn, through Lin and the domain. #然, if necessary, can be combined with sequential and synchronous dipping. Suitable gold bodies include, for example, metal pures, amine dissolved metal hydroxides, metal nitrate bismuth salts. For example, the cage compound of the tilting, including the chlorine paving gas, the oxidizing of the amine, the nitrous acid, the gas, the oxalic acid surface, the Gu Shi's four records, the gas, the oxalic acid, Gasify her and gasification. In general, an aqueous solution of a soluble compound is preferred, both economically and environmentally. In the embodiment - the 'metal precursor is not a metal and is substantially free of metal toothing 20 201121651. If not limited to theory 'this non-metal tooth precursor is considered to be an option to increase ethanol rate. A particularly preferred platinum precursor is tetraammonium nitrate platinum Pt(NH3)4(N〇4)2. In one aspect, "accelerators, metal or metal precursors are first added to the modified support, followed by the addition of "main" or "basic" metal or metal precursors. Of course, the reverse order of addition is also possible. Exemplary precursors of promoter metals include metal dentates, amine solubilized metal argon oxides, metal nitrates or metal oxalates. As described above, in sequential embodiments, after each impregnation step Preferably, drying and calcination are carried out. In the case of the above-mentioned promoted bimetallic catalyst, the metal may be impregnated in sequence, after the first addition of the promoter metal, the second impregnation step involves co-impregnation of two main metals, such as platinum and tin. For example, the preparation of PtSn/CaSi03 supported on SiO 2 consists of first impregnating CaSi03 to cerium oxide, followed by co-impregnation of Pt(NH3)4(N04)2 and Sn(AcO)2. Again, each The dipping step can be followed by a drying and satin burning step. In most cases, a metal nitrate solution can be used for the impregnation. However, other various soluble salts which can be released by calcination to release metal ions can also be used. With suitable soluble Examples of metal salts include metal acids such as perrhenic acid solutions, metal oxalates, etc. In the case of such substantially pure ethanol, it is generally preferred to avoid the use of a platinum group metal halide precursor, but to use nitrogen. Precursors of amines and/or nitrates. According to one embodiment of the invention, the hydrogenation of acetic acid to ethanol process can be carried out using a variety of configurations known to those skilled in the art - fixed bed reactors or fluidized bed reactors. In many embodiments of the invention, an "adiabatic" reactor can be used, that is, there is little or no need to pass an internal conduit to heat or remove heat in the reaction zone. Additionally, a shell with a heat transfer medium can be used. Reactors. In many cases, the reaction zone can be placed in a vessel or a series of vessels in which the heat exchanger is interposed. However, the use of the catalyst of the present invention for the acetic acid reduction process can be considered significant in the adiabatic reactor. Because this reactor configuration cost is typically much lower than the capital-intensive shell-and-shell configuration. Typically, the catalyst is used in a fixed-bed reactor. The reactor is, for example, in the shape of an elongated pipe or tube 21 201121651, wherein the reactants are typically passed in the form of a vapor, or passed through a catalyst. Other reactors, such as fluidized or bunk bed reactors, may be employed if desired. In some cases, the hydrogenation catalyst may be simultaneously provided with an inert material such as glass wool to adjust the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactant with the catalyst particles. The hydrogenation reaction may be carried out in the liquid phase or the gas phase. It is preferred to carry out the gas phase reaction under the following conditions: The reaction temperature may be from 125 ° C to 350. (:, for example, from 200 ° C to 325 ° (:, from 225 ° (: to 300 ° C, Or from 25 (TC to about 30 〇. 〇 pressure range from 1 〇 kPa (Kpa) to 3,000 kPa (about 0.1 to 30 atmospheres), for example, from 50 kPa to 2,300 kPa, or from 1 〇〇 Pa to 1,500 kPa·»reactant feed to the reactor, gas hourly space velocity GHSV) may be greater than 500 / hour, for example, greater than ι, 〇〇〇 / hour, greater than 2 5 〇〇 / hour Even greater than 5,0 mph. In terms of range, GHSV can range from 50/hour to 50,000/hour, for example, from 500/hour to 30.000/hour. • 〇〇〇 / hour to 1 〇 小时 / hour, or 1 〇〇〇 / hour to 6,500 / hour. In the remainder of the invention, the nitriding system is carried out under a pressure sufficient to overcome the pressure drop of the surface space through the catalytic bed, although the higher pressure is not disabled, it goes without saying that at high space velocities, For example, 5,000 / hour, or 6,500 / hour through the reactor bed may encounter a considerable pressure drop. Although two moles of hydrogen per mole of acetic acid reaction, the production of "mo-ethanol", the actual hydrogen in the feed stream to acetic acid The molar ratio may vary: about: 丨 to 丨: (10), for example, from 50: 1 to 1: 50, from 20: 1 to 丨: 2, or from 12: 丨 to 丨: Bu is best hydrogen The molar ratio to acetic acid is greater than 4: for example, greater than 5:1 or greater than 1 〇: Bu contact or residence time is also very different, depending on the amount of acetic acid, catalyst, reactor, temperature and pressure. Typical contact _ fines from less than 1 second to more than a few hours, ^ using a solid & bed-in-the-earth phase gas phase reaction preferred contact time is between at least about seconds and 100 seconds, for example, from 0.3 Up to 80 seconds or 0. 4 to 30 seconds. 22 201121651 The nature of the Wei body, such as = Syrian vinegar shoot _ Wei Cai _ face relatively lazy should be stolen. For gas phase reactions, the system should control the temperature to the dew point. The degree of proton is not lower than that of the acetic acid medium and the process, and good vinegar transfer and favorable selectivity and yield can be achieved. For the purposes of the present invention, conversion - the term refers to the ratio of acetic acid converted to acetic acid in the feed. Conversion rate is the amount of acetic acid in the feed = no. The acetic acid conversion rate is calculated by gas chromatography (GC) using the following formula = - acetic acid conversion rate (%) = 〇〇 _ * · [- vinegar _ acid __ _ mmol _ ( Feed stream)_[mmols of acetic acid] (exhaust stream) [mole of acetic acid] (feed stream) ^The purpose of the present 'conversion rate can be at least 1G%, for example, at least have at least milk% 'At least 5G%' has at least 6G%, at least 7 peaches, or at least _. Although it is desirable for the catalyst to have a higher rate, such as at least _ or at least writing, if there is a high selectivity for ethanol, the conversion is low. This is of course easy to understand in the case of T. 'The conversion rate can be compensated by appropriate circulation or by using a larger reactor, but it is more difficult to make up for the low selectivity. _ Selectivity rate, expressed as mole percent of converted acetic acid. It should be recognized that each of the compounds converted from acetic acid has a separate material, and the drunk is also independent of the conversion rate. For example, if 50 mole % of acetic acid is converted to ethanol, we mean that the selectivity of ethanol is high. The selectivity of ethanol is calculated by IU mesh chromatography (GC), which allows the calculation of the formula: Ethanol selectivity (〇/〇) = 丨〇〇 *___ millimoles of ethanol produced (GC) Box Chu Yan .. millimoles of carbon output (GO _ who is the molar enthalpy of vinegar in the berth (G<:) 23 201121651 where the "mole of the tiling (Gey) refers to gas chromatography The total millimoles of carbon in all products analyzed. For the purposes of the present invention, the ethoxylates selectivity of the catalyst is at least 60%, for example, at least 70%, or at least 80%. The term "ethoxy", as used, specifically refers to the compounds ethanol, acetaldehyde and ethyl acetate. Preferably, the selectivity to ethanol is above 8%, for example, at least 85% or at least 88%. In embodiments of the invention It is also preferred to have lower selectivity for undesired products such as methane, ethane and carbon dioxide. The selectivity of these undesirable products is less than 4% 'if less than 2% or less than 1%. Preferably, during the hydrogenation process, these undesirable products are detected. In some embodiments of the invention, the rate of formation of the smoke is low, usually Below 2%, often below 1%, and in many cases less than 0.5% of acetic acid is converted to alkanes by catalysts, while alkanes are of little value other than as fuel. Yield refers to per kilogram of hydrogenation during hydrogenation The number of grams of a particular product (e.g., ethanol) formed per hour by the medium. In the embodiment of the present invention, the yield is at least 2 (8) grams of ethanol per kilogram of contact time, for example, at least 4 grams per kilogram of catalyst per hour. Ethanol or preferably ethanol is at least 6 gram. In terms of range, the yield is preferably 2 (10) to 3, gram of ethanol per kilogram of catalyst per hour, for example '400 to 2, 5 gram or 600 To 2, gram of ethanol. Some of the catalysts of the invention can achieve a conversion of acetic acid of at least 1%, a selectivity to ethanol of at least 8 〇 ^ ' and a yield of at least 2 gram per hour of kilograms per kilogram of ethanol. A sub-population of the inventive catalyst can achieve at least a conversion of acetic acid, a selectivity to ethanol of at least 8 (%), a selectivity to undesirable compounds of less than 4%, and a yield of at least one kilogram per kilogram of alcohol. - Real money" 'The present invention provides a kind of B formed by the invention of the present invention Crude product. Prior to any subsequent processing (purification and separation), the crude ethanol product formed by the hydrogenation process of the present invention will typically comprise primarily unreacted acetic acid and ethanol. In some typical embodiments, the crude ethanol product comprises ethanol. The content is from 15% by weight to % by weight based on the total weight of the crude ethanol product. 24 201121651 Amount % 'for example, 20% by weight to 50% by weight ' or from 25% by weight to % by weight. Preferably, the crude ethanol product contains at least 22% by weight. Ethanol, at least 28% by weight of ethanol or at least 44% by weight of ethanol. The crude ethanol product will generally include unreacted acetic acid, depending on the conversion, for example, from 〇 to 8G% by weight, for example, from 5 to 8 ()% by weight, from 2〇 to 7〇«%, from 28 to 7〇 heavy Wei or from Μ to & Since water is formed in the reaction process, water will also be present in the crude ethanol product, for example, from 5 to % by weight, for example, from K) to 3% by weight or from 1 to 26% [other ingredients, for example, Vinegar and carbon dioxide, if detected, may be less than ι by weight, for example, less than 6% by weight or less than 4% by weight. In terms of ranges, the other component contents are from Μ to 1G repetitive frequency', e.g., from (4) 6% by weight, or from 4 to 4 weights. In various embodiments of the invention, the exemplary composition of the crude ethanol product is listed in Table 2 below. Table 2 Composition concentration of crude ethanol (% by weight) Concentration (weight (degree of weight / 〇) concentration, 壬 true 0 /, ethanol acetic acid water other 15-70 5-80 5-30 <10 15- 70 20-70 5-30 <10 20-50 28-70 10-30 <6 -----, Li Dong y〇) 25-50 44-65 10-26 _ <4 25 201121651 Table 3 Constituent composition of crude ethanol product A concentration (weight 〇 / 0) composition B concentration (% by weight) composition C concentration (weight ° / 〇) 17 26 45 74 53 20 7 13 25 2 8 10 ethanol acetic acid water

用^本發鄕㈣補可縣自任何合適的來源 ，包括天然氣，石油， 煤厌’生物料等。這是眾所周知的，通過甲醇艘基化，乙链氧化，乙稀 氧化’氧化發酵’厭氧發料，可生產醋酸。由於石油和天然氣變得波 動價格忽起忽落’用於從備用碳源生產醋酸和巾間體如甲醇和—氧化 石及的方法’已引起越來越大的興趣。特別是，當石油價格比天然氣較高 時由任何合適的碳源所衍生的合成氣（“syn gas”）生產醋酸可能成 為有利。例如Vidalin氏美國專利第6,232,352號揭露改裝甲醇廠以生產 醋酸的方法，可納入做為參考。通過改裝甲醇廠，可顯著減少或大部分 消除新醋酸廠產生一氧化碳的所需的大型資本成本。由f醇合成循環轉 出全部或部分合成氣，並提供給回收一氧化碳和氫氣單元，然後再用於 生產醋酸。除了醋酸，這個製程也可以用來製造本發明有應用關連之氫 氣0Use this hairpin (4) to make up the county from any suitable source, including natural gas, petroleum, coal, and biomaterials. It is well known that acetic acid can be produced by methanol chaining, ethylene chain oxidation, ethylene oxidation, oxidative fermentation, and anaerobic delivery. As oil and natural gas become volatile, the 'method of producing acetic acid and towel bodies such as methanol and oxidized stone from alternate carbon sources' has attracted increasing interest. In particular, it may be advantageous to produce acetic acid ("syn gas") derived from any suitable carbon source when the price of oil is higher than natural gas. For example, U.S. Patent No. 6,232,352 to the disclosure of U.S. Pat. By retrofitting the methanol plant, the large capital cost required to eliminate carbon monoxide from the new acetic acid plant can be significantly reduced or largely eliminated. All or part of the synthesis gas is recycled from the f-alcohol synthesis cycle and supplied to the recovery of carbon monoxide and hydrogen units, which are then used to produce acetic acid. In addition to acetic acid, this process can also be used to make hydrogen gas for applications of the present invention.

Steinberg等氏美國再發證專利號re 35,377 ’此處也納入參考，提供— 種由炭素物料，如石油，煤炭，天然氣和生物料轉化成甲醇之方法。這 個製程包括固體和/或液體炭素物料氫化氣化獲取製程氣的方法，該製 程氣進一步另加入天然氣，進行蒸汽熱解以形成合成氣。該合成氣轉化 為曱醇，再使甲醇叛化可得醋酸。該方法也同樣產生氫氣，而氫氣可如 上所述用於本發明中。另見Gra办等氏美國專利第5,821，111號，其中 26 201121651 公開一種錢錄_化製程，通職歸齡錢，以細^等氏 美國專利第6,685,754號之揭露，均在此納入參考。 另外’蒸氣形式的醋酸可從f醇幾化單元之閃蒸塔直接做為粗製品，參 $氏美國專利第6,657,〇78號中所描述其全文在此納入參考。 蒸氣粗產物可直接獻本發贩舰，柯需要聽和健份或移 除水’節約整體處理成本。 ^發明H化製崎獲得⑽可以自己直接㈣為燃料或轉作乙稀，其為 疋-種重要的大宗商品的原料’因為它可以轉化為聚乙稀，醋酸乙稀醋 和/或醋酸乙醋或任何其他多種化工產品。例>，乙稀也可以轉換為眾 多的聚合物和單體產品。乙醇脫水製乙烯如下式所示。 任何已知的脫水觸媒可用於乙醇脫水，如正在一起申請專利的美國申請 號12/221,137和美國的申請號12/221,138所描述，其全部内容及揭露在 此納入參考。沸石觸媒，例如，可用作為脫水觸媒。可以使用孔徑至少 約0.6奈米的任何沸石，較佳沸石包括脫水觸媒，其選自包含絲光沸石 (mordenites) ’ ZSM - 5 ’沸石X和沸石γ之群組。沸石χ ’例如，記載 於美國專利第2,882,244號和Y型沸石記載於美國專利第3，13〇,〇〇7號， 其全部内容在此納入參考。 乙醇也可作為燃料，藥品，清潔劑，消毒劑，氫化傳輸(hydr〇genati〇n transport)或消耗品。乙醇也可用來製作醋酸乙酯，乙醛，高級醇，尤其 是丁醇之原料。此外，根據本發明於製造乙醇的製程中所形成之任何 酯，如醋酸乙酯等，可進一步與酸觸媒反應，形成額外的乙醇以及醋酸， 後者可回收到氫化製程。 玆參照下面眾多實施例詳細說明本發明’其目的僅供舉例及說明之用。 27 201121651 在本發明下狀中請專織_之_及細崎實施例所作之修改 對此領域之熟習技藝者而言係顯而易，均仍屬於本發明範圍内。 下面的實施例描述本發明製程中所用各種觸媒的製備方法。 【實施方式】 觸媒的Μ備（一船) 觸媒支碰在《空氣下於丨耽賴過夜後找仙。除非另有提 及’所有的商業使用支雜（亦即二氡化石夕、氧化鍅）尺寸為削網 目(mesh) ’或以其原來的形狀（1/16英寸或1/8英寸顆粒）均可使用。 添加金屬後’粉狀物料（即可經造粒、辨和。個別觸 媒的製備在下列章節中將詳細介紹。 實施例 1 - SiO^-CaSiOt⑸-Pt(3VSnn.8押畔 該觸媒之製備包含首先在二氧化销敎雜巾加人⑽仙（Aldrfch 公司），其次是加入鉑/錫。先製備偏矽酸約CaSi〇3 g 2〇〇網目）的水 相懸浮液，包含在13毫升去離子水中加入0.52克此偏矽酸約固體，其 次加入1.〇毫升的膠體二氧化矽（15重量％的溶液，NALC〇公司）。在 至，孤攪拌懸浮液2小時，然後使用，’初濕技術，，wetness teehniquej 加到10.0克的二氧化碎觸媒支撐體（14/30網目）。放置2個小時後， 蒸發該材料至乾固，接著在循環空氣下於12(TC乾燥過夜，和在50(rc 锻燒6小時。然後所有的si〇rCaSi〇3材料用於鉑/錫金屬浸潰。 觸媒的製備包含先在含有6.75毫升1 : 1稀釋的冰醋酸（Fisher公司） 小瓶中加入Sn(OAc)2 (醋酸錫，購自Aldrich公司）（0.4104克，1.73 毫摩爾）。在室溫將混合物授拌15分鐘’然後加入0.6711克（1·73亳 摩爾）固態Pt(NH3)4(N〇3)2 (Aldrich公司）。在室溫再將混合物攪拌15 分鐘，然後滴入在100毫升圓底燒瓶中之5.0克SiOrCaSi03支撐體。 不斷授拌金屬溶液’直到所有的銘/錫混合物已添加到Si〇2-CaSi03支揮 28 201121651 體，其中每次添加金屬溶液後，均旋轉燒瓶。完成添加金屬溶液後，在 室溫放置含有浸潰觸媒之瓶子兩小時。然後燒瓶連接到轉子蒸發器（浴 溫度80°C) ’並在燒瓶旋轉之情況下抽氣至乾固。隨後該材料進一步在 120°C乾燥過夜’接著使用下列程序升溫煅燒：25°c — 16〇。(：/梯度5.〇°c/ 分鐘；保持有2.0小時；160°C4 500°C/梯度2.0eC/分鐘；保持4小時。 產量：11.21克深灰色的材料。 實施例 2-KA160-CaSiO,⑻4 該材料製備包含先在KA160觸媒支撐體（Si〇2_(0.05) Al2〇3, Sud Chemie 公司，14/30網目）中加入CaSiCb，其次是加入鉑/錫。首先，製備CaSi〇3 (S200網目）的水相懸浮液，包含在3 85毫升去離子水中加入〇 42克此 CaSiCb固體，其次加入〇.85毫升的膠體二氧化石夕（15重量％的溶液， NALCO公司）。在室溫攪拌懸浮液2小時，然後使用初濕技術加到$ 〇 克的KA160觸媒載體（14/30網目）中。放置2個小時後，蒸發該材料 至乾固，接著在循環空氣下於12〇°C乾燥過夜，和在500。(：烺燒6小時。 然後所有的KA160-CaSiO3材料用於翻/錫金屬浸潰。 觸媒的製備包含先在含有6.75毫升1 ·· 1稀釋的冰醋酸（Fisher公司） 之小瓶中加入Sn(OAc)2 (醋酸錫，購自Aldrich公司）（0.2040克，0.86 毫摩爾）。在室溫將混合物攪拌15分鐘，然後加入〇 335〇克（〇 86毫 摩爾）固態Pt(NH3)4(N〇3)2 ( Aldrich公司）。在室溫再將混合物攪拌15 刀鐘’然後滴入在1〇〇毫升圓底燒瓶中之5 〇克Si〇rcasi〇3支樓體。 完成添加金屬溶液後，在室溫放置含有浸潰觸媒之瓶子兩小時。然後燒 瓶連接到轉子紐^ (浴溫度贼），並在紐麟燒瓶之情況下抽氣 至乾固。隨後該材料進一步在n〇〇c乾燥過夜，接著使用下列程序升溫 煅燒· 25~> 160。(：/梯度5.0°C/分鐘；保持有2.0小時；160— 500。(：/梯度 2·〇 C/分鐘；保持4小時。產量：5 19克棕褐色的材料。 29 201121651 實施例 3 - SiOi-CaSiOW.SVPtn.SVSniO.^ 依照實施例1相同的方式製備觸媒，但原料為：0.26克CaSi03(作為支 樓體改性劑）’0·5毫升的膠·體二氧化;e夕（15重量％溶液，NALCO公司）， 〇.3355 克（〇·86 毫摩爾）Pt(NH3)4(N〇3)2 ;及 0.2〇52 克（0.86 毫摩爾） Sn(OAc)2 (醋酸錫）。產量：10.90克深灰色的材料。 實施例 4 - Si〇, + MgSiO,-Ptn.m-Snf1.cn 依照實施例1相同的方式製備觸媒，但原料為：0.69克醋酸錢(作為支 撐體改性劑）；1.3克膠體二氧化矽（15重量％溶液，NALCO公司）， 0.2680 克（0.86 毫摩爾）Pt_3)4(N〇3)2 ;及 0.164〇 克（0.86 毫摩爾） Sn(OAc)2 (醋酸錫）。產量：8.35克。Si〇2支樓體浸潰於醋酸鎂的和膠 體二氧化矽之溶液。乾燥支撐體，然後煅燒至700°C。 實施例 5- Si〇2-CaSiOJ5VRensVPiim 依照實施例1的方式製備Si〇2_CaSi〇3(5)改性觸媒支撐體。然後製備銖 /把觸媒，包含以NHjReO4和Pd(N〇3)2的水溶液浸潰Si〇2_CaSi〇3(5) (1/16英寸擠出體）。金屬溶液的製備，包含先在含有12 〇毫升去離子 水的小瓶中加入NKtReCXj (0.7237克，2.70毫摩爾）。在室溫攪拌混合 物15分鐘’然後加入an%克（〇/76毫摩爾）固態Pd(N03)2。在室溫 攪拌混合物15分鐘，然後滴入在100毫升圓底燒瓶1〇〇克乾燥的 Si〇r(〇.〇5)CaSi〇3觸媒支撐體。完成金屬溶液添加後，在室溫放置含有 浸潰觸媒之燒瓶兩小時。所有其他操作（乾燥，煅燒）均依照實施例j 所述的步驟進行。產量：10.9克褐色物質。 f 施例 6 - Si07-ZnO(^)-Pt⑴-Snfl) 在120 °C供箱及大氣循環下乾燥粉末狀和篩析過的粒徑分佈均勻約〇 2 毫米之高表面積二氧化矽NPSG SS61138 (100克）過夜，然後冷卻到 室溫。在此二氧化矽中加入硝酸鋅六水合物溶液。由此產生的泥漿在烤 箱中逐漸加熱至1UTC (>2小時，lot/分鐘）乾燥之，然後煅燒。又 201121651 ^中加入石肖酸翻（chempur公司）/蒸德水之溶液和草酸锡（施心咖 :(丨.74 g) /稀硝酸（1N，8.5毫升）之溶液。在逐步加熱到ll〇°C >2小時’ 10 °c/分鐘）之烤箱中乾燥所產生的泥梁。然後在5酿锻 燒此浸潰觸媒混合物（6小時，分鐘）。 此外’亦製備下面的比較觸媒。Steinberg et al., Reissued Patent No. 35,377' is also incorporated herein by reference for the provision of a method for the conversion of carbonaceous materials such as petroleum, coal, natural gas and biomass into methanol. This process includes a method of hydrogenating a solid and/or liquid carbon material to obtain a process gas, which is further added to natural gas for steam pyrolysis to form a syngas. The syngas is converted to decyl alcohol, which is then regenerated by methanol to give acetic acid. The process also produces hydrogen as well, and hydrogen can be used in the present invention as described above. See also, U.S. Patent No. 5,821,111, the disclosure of which is incorporated herein by reference. Further, the acetic acid in the form of a vapor can be directly used as a crude product from the flash column of the dealcoholization unit, as described in U.S. Patent No. 6,657, the entire disclosure of which is incorporated herein by reference. The crude vapor product can be directly distributed to the ship, and Ke needs to listen to and protect or remove water' to save overall processing costs. ^Invented H-Chemistry to obtain (10) can directly (four) as fuel or convert to ethylene, which is the raw material of 疋-an important commodity 'because it can be converted into polyethylene, ethyl acetate and / or acetic acid Vinegar or any other variety of chemical products. Example >, Ethylene can also be converted into a wide range of polymers and monomer products. Dehydration of ethanol to ethylene is shown in the following formula. Any of the known dehydration catalysts can be used for the dehydration of ethanol, as described in U.S. Patent Application Serial No. 12/221,137, the entire disclosure of which is incorporated herein by reference. Zeolite catalysts, for example, can be used as dehydration catalysts. Any zeolite having a pore size of at least about 0.6 nm can be used. Preferably, the zeolite comprises a dehydration catalyst selected from the group consisting of mordenites 'ZSM-5' zeolite X and zeolite gamma. The zeolite χ ' is described, for example, in U.S. Patent No. 2,882,244, and the Y-type zeolite is described in U.S. Patent No. 3,13, the entire disclosure of which is incorporated herein by reference. Ethanol can also be used as a fuel, a drug, a detergent, a disinfectant, a hydrolyzed transport or a consumable. Ethanol can also be used to make ethyl acetate, acetaldehyde, higher alcohols, especially butanol. Further, any ester formed in the process for producing ethanol according to the present invention, such as ethyl acetate or the like, can be further reacted with an acid catalyst to form additional ethanol and acetic acid, which can be recycled to the hydrogenation process. The present invention has been described in detail with reference to the embodiments herein below. It is obvious to those skilled in the art that it is obvious to those skilled in the art that it is within the scope of the present invention. The following examples describe the preparation of various catalysts used in the process of the present invention. [Embodiment] Catalyst preparation (one boat) The catalyst is touched in the air to find the fairy after spending the night. Unless otherwise mentioned, 'all commercial use (ie, two-dimensional fossil, yttrium oxide) size is meshed 'or in its original shape (1/16 inch or 1/8 inch particle) be usable. After adding metal, the powdery material can be granulated and identified. The preparation of individual catalysts will be described in detail in the following sections. Example 1 - SiO^-CaSiOt(5)-Pt (3VSnn.8 Preparation of an aqueous suspension comprising the first addition of a doped bismuth wipe (10) sen (Aldrfch), followed by the addition of platinum/tin. First prepared a bismuth decanoic acid about CaSi 〇 3 g 2 〇〇 mesh), contained in 13 0.52 g of this citric acid was added to the deionized water to a solid, followed by 1. 〇ml of colloidal cerium oxide (15% by weight solution, NALC®). At that time, the suspension was stirred for 2 hours and then used. 'Incipient wetness technology, wealth teehniquej was added to 10.0 g of the dioxide catalyst support (14/30 mesh). After standing for 2 hours, the material was evaporated to dryness, followed by circulating air at 12 (TC drying). Overnight, and calcined at 50 (rc for 6 hours. Then all si〇rCaSi〇3 materials were used for platinum/tin metal impregnation. The catalyst was prepared by first containing 6.7 g of 1:1 diluted glacial acetic acid (Fisher) ) Sn(OAc) 2 (tin acetate, purchased from Aldrich) was added to the vial ( 0.4104 g, 1.73 mmol). Mix the mixture for 15 minutes at room temperature' then add 0.6711 g (1.73 mol) of solid Pt(NH3)4(N〇3)2 (Aldrich). The mixture was stirred for 15 minutes and then dropped into 5.0 g of SiOrCaSi03 support in a 100 ml round bottom flask. The metal solution was continuously mixed until all the ingot/tin mixtures had been added to the Si〇2-CaSi03 fulminator 28 201121651 body, After each addition of the metal solution, the flask was rotated. After the addition of the metal solution was completed, the bottle containing the impregnated catalyst was placed at room temperature for two hours. Then the flask was connected to a rotor evaporator (bath temperature 80 ° C) 'and in the flask The air was pumped to dryness in the case of rotation. The material was then further dried at 120 ° C overnight. Then the calcination was carried out using the following procedure: 25 ° c - 16 〇. (: / gradient 5. 〇 ° c / min; Hour; 160 ° C 4 500 ° C / gradient 2.0 eC / min; hold for 4 hours. Yield: 11.21 g of dark gray material. Example 2 - KA160-CaSiO, (8) 4 The material was prepared to contain the KA160 catalyst support (Si 〇2_(0.05) Al2〇3, Sud Chemie, 14/30 Add CaSiCb, followed by platinum/tin. First, prepare an aqueous suspension of CaSi〇3 (S200 mesh) containing 42 grams of this CaSiCb solid in 3 85 ml of deionized water, followed by 〇.85 ML of colloidal silica dioxide (15% by weight solution, NALCO). The suspension was stirred at room temperature for 2 hours and then added to a gram of KA160 catalyst carrier (14/30 mesh) using incipient wetness techniques. After standing for 2 hours, the material was evaporated to dryness, then dried overnight at 12 ° C under circulating air, and at 500. (: simmer for 6 hours. Then all KA160-CaSiO3 materials were used for flip/tin metal impregnation. The catalyst was prepared by adding Sn to a vial containing 6.75 ml of 1 ··1 diluted glacial acetic acid (Fisher). (OAc) 2 (tin acetate, purchased from Aldrich) (0.2040 g, 0.86 mmol). The mixture was stirred at room temperature for 15 minutes, then 〇335 g (〇86 mmol) of solid Pt(NH3)4 ( N〇3)2 (Aldrich). Stir the mixture for 15 knives at room temperature and then drip into the 5 gram Si〇rcasi〇 3 building in a 1 liter round bottom flask. Thereafter, the bottle containing the impregnated catalyst was placed at room temperature for two hours. The flask was then attached to the rotor (bath temperature thief) and pumped to dryness in the case of the Newlin flask. The material was then further n n 〇c was dried overnight, and then calcined using the following procedure: 25~> 160. (:/gradient 5.0 ° C / min; maintained for 2.0 hours; 160 - 500. (: / gradient 2 · 〇 C / min; Hour. Yield: 5 19 g of tan material. 29 201121651 Example 3 - SiOi-CaSiOW.SVPtn.S VSniO.^ The catalyst was prepared in the same manner as in Example 1, except that the raw material was: 0.26 g of CaSi03 (as a building block modifier) '0.5 ml of colloidal body dioxide; e-night (15% by weight solution, NALCO), 355.3355 g (〇·86 mmol) Pt(NH3)4(N〇3)2; and 0.2〇52 g (0.86 mmol) Sn(OAc)2 (tin acetate). Yield: 10.90 a dark gray material. Example 4 - Si〇, + MgSiO, -Ptn.m-Snf1.cn A catalyst was prepared in the same manner as in Example 1, but the starting material was: 0.69 g of acetic acid (as a support modifier) 1.3 g colloidal ceria (15 wt% solution, NALCO), 0.2680 g (0.86 mmol) Pt_3) 4 (N〇3) 2 ; and 0.164 g (0.86 mmol) Sn(OAc) 2 ( Tin acetate). Yield: 8.35 g. The Si〇2 branch was impregnated with a solution of magnesium acetate and colloidal ceria. The support was dried and then calcined to 700 ° C. Example 5 - Si〇2-CaSiOJ5VRensVPiim A Si〇2_CaSi〇3(5) modified catalyst support was prepared in the same manner as in Example 1. Then, a ruthenium/catalyst was prepared, and the Si〇2_CaSi was impregnated with an aqueous solution of NHjReO4 and Pd(N〇3)2. 〇 3 (5) (1/16 inch extrudate). The metal solution was prepared by first adding NKtReCXj (0.7237 g, 2.70 mmol) to a vial containing 12 mL of deionized water. The mixture was stirred at room temperature for 15 minutes' then an gram (?/76 mmol) of solid Pd(N03)2 was added. The mixture was stirred at room temperature for 15 minutes, and then dropped into a 100 ml round bottom flask, 1 g of a dried Si〇r(〇.〇5) CaSi〇3 catalyst support. After the completion of the addition of the metal solution, the flask containing the impregnated catalyst was placed at room temperature for two hours. All other operations (drying, calcination) were carried out in accordance with the procedure described in Example j. Yield: 10.9 g of brown material. f Example 6 - Si07-ZnO(^)-Pt(1)-Snfl) Dry powdered and sieved high-surface area cerium oxide NPSG SS61138 with a uniform particle size distribution of about 2 mm at 120 °C in a tank and atmospheric circulation (100 g) overnight and then cooled to room temperature. A zinc nitrate hexahydrate solution was added to the cerium oxide. The resulting slurry was gradually heated to 1 UTC (> 2 hours, lot/min) in a roasting oven and then calcined. Also in 201121651 ^ added a solution of sulphuric acid (chempur) / steamed water and tin oxalate (Shi Xin coffee: (丨.74 g) / dilute nitric acid (1N, 8.5 ml) solution.泥 ° C > 2 hours '10 °c / min) in the oven to produce the mud beam. The impregnated catalyst mixture (6 hours, minutes) was then fired in 5 batches. In addition, the following comparative catalysts were also prepared.

翻教1·^觸媒:Ii〇2=£aSiO科p“3、-Sn“.8V 該材料的製備包含先在Ti〇2觸媒（銳钦型，14/30,網目）支樓體中加入 CaSK^ ’其次加入實施例丨所描述的銘/錫^首先，製備c板〇3 口 2〇〇 網目）的水相财液，包含在7.〇毫升去料水巾加人炫克此CaSi〇3 固體，其次加入1.0毫升的膠體二氧化矽（15重量％的溶液，nalc〇 ，司）°在室溫麟懸浮液2小時’然後使用初濕技術加到则克的二 氧化鈦觸媒支M/3G網目）卜放置2個小時後，蒸發該材料至 乾固’接著在循環空氣下於UOt乾燥過夜，和在复⑽燒6小時。 然後依照f齡丨1所述的步驟，使所有的Ti〇rCaSi()3；N_细於麵/錫金 屬浸潰，其中使用0.6711克PtCNHA^O3)2和0.4104克（i 73毫摩爾） Sn(OAc)2 (醋酸錫）。產量：u 5克淺灰色材料。Teach 1·^ Catalyst: Ii〇2=£aSiO Section p “3,-Sn”.8V The preparation of this material consists of a Ti〇2 catalyst (Ruiqin type, 14/30, mesh) Add CaSK^' followed by the description of the inscription / tin described in the example 首先 first, prepare the c-plate 〇 3 mouth 2 〇〇 mesh) water phase of the liquid, contained in 7. 〇 ml to the water towel add people This CaSi〇3 solid, followed by the addition of 1.0 ml of colloidal cerium oxide (15% by weight solution, nalc 〇, 司) ° at room temperature for a suspension of Lin for 2 hours ' then added to the gram of titanium dioxide catalyst using incipient wetness techniques After the M/3G mesh was placed for 2 hours, the material was evaporated to dryness, then dried overnight in UOt under circulating air, and burned at complex (10) for 6 hours. Then, according to the procedure described in F age 1, all Ti〇rCaSi()3; N_ is finer than the face/tin metal, wherein 0.6711 g of PtCNHA^O3)2 and 0.4104 g (i 73 mmol) are used. Sn(OAc)2 (tin acetate). Yield: u 5 g light gray material.

在120°C烘箱及氮氣循環下乾燥粉末狀和篩析過的粒徑分佈均勻約 0.2 毫米之高純度度低表面積二氧化碎（克）過夜，然後冷卻到室溫。 在此二氧化矽中加入草酸錫(AlfaAesar公司）在稀硝酸（1N，85毫升） 溶液。由此產生的泥漿在烤箱中逐漸加熱至110。〇（>2小時nz分 鐘）乾燥之’然後在500t煅燒（6小時，It：/分鐘）。 實施例9 -比較觸媒一承載於高表面稽二氣化矽Η的pt(2KSn〇 在120°C烘箱及大氣循環下乾燥粉末狀和篩析過的粒徑分佈均勻約〇2 毫米之高表面積二氧化矽NPSG SS61138 (1〇〇克）過夜，然後冷卻到 室溫。在此二氧化矽中加入硝酸鹽六水合物(Chempuf公司)溶液。由此 201121651 產生的泥漿在烤箱中逐漸加熱至110°c (>2小時，lot/分鐘）乾燥之， 然後锻燒。又在其中加入硝酸鉑（Chempur公司）/蒸餾水之溶液和草 酸錫（AlfaAesar公司）/稀硝酸之溶液。在逐步加熱到11〇«c (>2小時， l〇°C/分鐘）之烤箱中乾燥所產生的泥漿。然後在500〇c煅燒此浸潰觸媒 混合物（6小時，rc/分鐘）。The powdery and sieved high purity low surface area dioxide granules (g) having a particle size distribution of about 0.2 mm were dried overnight at 120 ° C in an oven and nitrogen cycle, and then cooled to room temperature. To this cerium oxide was added a solution of tin oxalate (Alfa Aesar) in dilute nitric acid (1 N, 85 ml). The resulting slurry is gradually heated to 110 in the oven. 〇 (> 2 hours nz minutes) dried 'and then calcined at 500t (6 hours, It: / minute). Example 9 - Comparing Catalyst pt on a high surface bismuth gasification ( (2KSn〇 is dried at 120 ° C in an oven and atmospheric circulation, and the particle size distribution is uniform and the particle size distribution is about 2 mm. Surface area of cerium oxide NPSG SS61138 (1 gram) overnight, and then cooled to room temperature. A solution of nitrate hexahydrate (Chempuf) was added to the cerium oxide. The slurry produced by 201121651 was gradually heated in the oven to 110 °c (> 2 hours, lot/min) was dried, then calcined, and a solution of platinum nitrate (Chempur) / distilled water and tin oxalate (Alfa Aesar) / dilute nitric acid was added thereto. The resulting slurry was dried in an oven of 11 〇 «c (> 2 hours, l 〇 ° C/min). The impregnated catalyst mixture was then calcined at 500 〇c (6 hours, rc/min).

實施例10 _比較觸媒-KA160-Ptmsnp A 依照實施例1所述之初濕浸潰步驟製備材料，但採用KA160觸媒支樓 體(SiOr(0.〇5) Α1ζ〇3，SudChemie公司，H/3〇網網目）。金屬溶液之製 備包含先在含有4.75毫升1 : 1稀釋的冰醋酸之小瓶中加入Sn(〇Ac)2 (醋酸錫’ 0.2040克’ 0.86毫摩爾）。在室溫將混合物攪拌15分鐘，然 後加入0.3350克（0.86毫摩爾）固態pt(NH3)4(N〇3)2。在室溫再將混合 物攪拌15分鐘，然後滴入在1〇〇毫升圓底燒瓶中之5 〇克尺八16〇觸媒 支撐體中。依照實施例1所述的步驟進行所有其他操作，包含乾燥和煅 燒。產量：5.23克，棕褐色的材料。Example 10 _Comparison Catalyst-KA160-Ptmsnp A The material was prepared according to the incipient wetness immersion step described in Example 1, but using a KA160 catalyst support body (SiOr(0.〇5) Α1ζ〇3, SudChemie, H/3〇网网). The metal solution was prepared by first adding Sn(〇Ac) 2 (tin acetate '0.2040 g' 0.86 mmol) to a vial containing 4.75 ml of a 1:1 diluted glacial acetic acid. The mixture was stirred at room temperature for 15 minutes and then 0.3350 g (0.86 mmol) of solid pt(NH3)4(N〇3)2 was added. The mixture was stirred for a further 15 minutes at room temperature and then added dropwise to a 5 〇 八 8 16 〇 catalyst support in a 1 〇〇 ml round bottom flask. All other operations, including drying and calcining, were carried out in accordance with the procedure described in Example 1. Yield: 5.23 g, tan material.

實_施例 11 -比較觸媒 SiO，-SnO<>⑸·Ptn~)_7,n(O 在120C烘箱及大氣循環下乾燥粉末狀和篩析過的粒徑分佈均勻約ο.〗 毫米之咼表面積二氧化矽NPSG SS61138 (1〇〇克）過夜，然後冷卻到 室溫。在此二氧化矽中加入醋酸錫溶液。由此產生的泥漿在烤箱中逐漸 加熱至110 C (>2小時，l〇°c/分鐘）乾燥之，然後烺燒。又在其中加 入硝酸銘（Chempur公司）/蒸傲水之溶液和草酸錫（趣八卿公司） /稀硝酸之溶液。在逐步加熱到11〇°C (>2小時，1〇〇c/分鐘）之烤箱中 乾燥所產生的雜。然後在5W：職此浸_麻合物（M、時，rc/ 分鐘）^ 宜熟例12-比較觸媒二8丨〇2_1[1〇，(他_1>心_<；!1^， 二氧化敛改性的支撐體之製備如下。在丨⑻毫升關底燒瓶中1〇〇克 Si〇2觸媒支碰（1/16英寸擠壓體）滴入415克（14·6毫摩爾） 32 201121651Real_Example 11 -Comparison of catalyst SiO,-SnO<>(5)·Ptn~)_7,n(O) Dry powdered and sieved particle size distribution in a 120C oven and atmospheric circulation is uniform ο. The surface area of cerium oxide NPSG SS61138 (1 gram) was left overnight, and then cooled to room temperature. A tin acetate solution was added to the cerium oxide. The resulting slurry was gradually heated to 110 C in the oven (>2 Hours, l〇 °c / min) dry, then simmer. Also add nitric acid (Chempur) / steamed water solution and oxalic acid tin (Mishuangqing company) / dilute nitric acid solution. Dissolve the resulting impurities in an oven at 11 ° C (> 2 hours, 1 〇〇 c / min). Then at 5W: dip _ hemp compound (M, hour, rc / min) ^ Example 12 - Comparison of Catalyst 2 8 丨〇 2_1 [1 〇, (He _1 > Heart _<;! 1^, Preparation of Dioxide-Condensed Modified Support as follows. In 丨(8) ml of the bottoming flask 1 〇〇克〇2〇 catalyst support (1/16 inch extrusion) drops 415 grams (14·6 mmol) 32 201121651

Ti{OCH(CH3)2}4 /2-異丙醇（14毫升）之溶液。在室溫放置燒瓶兩小時， 二後藉由轉子蒸發H (浴溫8〇。〇抽氣至乾固。接下來，在燒瓶中緩 慢加入2G毫升去離子水，並放置此材料ls分鐘。接著過駐除由此產 生的水/2-異丙醇’並再重複兩次添加水。最後在l2〇(>c循環空氣下乾燥 材料過夜，然後於5〇〇t烺燒6小時。隨後依照實施例！所述的步驟， 使所有的二氧化矽_二氧化鈦材料用於鉑/錫金屬浸潰，但使用〇67ΐι克 (1.73毫摩爾）和〇 41〇4克（丨73毫摩爾）醋酸鎖。產 量：11.98克深灰色1/16英寸的擠壓體。 复施例 13-比較觸媒 _SiO”w〇l(l0vptr》_Sn(1 二氧化鎢改性的二氧化矽支撐體之製備如下。在丨⑻毫升圓底燒瓶中 10.0克的二氧化石夕NPSGSS 61138觸媒支撐體（表面積=250平方米/ 克，1/16英寸擠壓體）滴加L24克(0.42毫摩爾）(NH4)6H2WI204〇 · ηΗ20, (AMT公司)/去離子水（14毫升）之溶液。在室溫放置燒瓶兩小時，然 後轉移到使用轉子蒸發器（浴溫度8(TC)抽氣至乾固。由此產生的材 料在120 C循環空氣乾燥過夜，其次在5〇〇°c锻燒6小時。然後依照上 述實施例1所述的步驟’使所有的（淺黃色）Si〇2_w〇3材料用於鉑/錫 金屬浸潰，但使用0.6711克（1/73毫摩爾）Pt(NH3)4(N〇3)2和〇.41〇4克 (I.73毫摩爾）醋酸錫。產量：12.10克深灰色丨/ 16英寸的擠壓體。 宜與例I4 -藉由實疼例W3觸媒進行醋酸氤化和乙薛袓製品之氣相屉 析（GC)分折 測試實施例1-13觸媒，以確定對乙醇的選擇率和產率，如表4所示。 蒸發醋酸反應料進料液，並和作為載氣的氫及氦一起加入反應器，合併 之平均每小時氣體空間流速（GHSV)，溫度及壓力，列於表4。進料流 中醋酸對氫之摩爾比如表4所示。 經由線上氣相層析儀分析產品（粗製乙醇組成物）。採用具一支火焰離 子化檢測器（FID)和兩支導熱探測器（TCDS)之三通道小型氣相層析 33 201121651 儀來分析反應物和產品。前面的通道配備了一支FID(火焰離子化檢測 器)和一支CP-Sil5 (20米）+ WaxFFap(5米）圓柱，用來定量：乙醛， 乙醇，丙酮，醋酸甲酯，醋酸乙烯酯，醋酸乙酯，醋酸，乙二醇二醋酸 酯，乙二醇，乙叉二醋酸酯和三聚乙醛。中間的通道配備一支TCD(導 熱探測器)和PorabondQ圓柱，用來定量：二氧化碳，乙烯和乙烷。背 面的通道配備一支TCD和Molsieve 5A圓柱，並進行定量：氦氣，氫 氣，氮氣，甲院和一氧化碳。 反應之前，藉由不同成分示踪劑測定各別化合物的滯留時間，與藉由已 知組成的標定氣體或已知組成的液體溶液校準氣相層析法儀。如此可測 定各種成分之反應因子。 34 201121651A solution of Ti{OCH(CH3)2}4 /2-isopropanol (14 ml). The flask was placed at room temperature for two hours, and then evaporated by a rotor (H) (bath temperature 8 Torr. 〇 evacuated to dryness. Next, 2 G of deionized water was slowly added to the flask and the material was placed for ls minutes. The water/2-isopropanol produced was removed and the water was added twice more. Finally, the material was dried overnight in a circulating air of l2 (>c, then calcined at 5 °t for 6 hours. In accordance with the procedure described in the examples!, all of the ceria-titanium dioxide material was used for platinum/tin metal impregnation, but using 〇67ΐιg (1.73 mmol) and 〇41〇4 g (丨73 mmol) of acetic acid. Yield: 11.98 g of dark gray 1/16 inch extruded body. Example 13 - Comparison of catalyst _SiO"w〇l (l0vptr)_Sn (1 preparation of tungsten dioxide modified cerium oxide support As follows: 10.0 g of a cerium oxide NPSGSS 61138 catalyst support (surface area = 250 m 2 /g, 1/16 inch extrudate) was added dropwise L24 g (0.42 mmol) in a 丨(8) ml round bottom flask ( NH4)6H2WI204〇·ηΗ20, (AMT)/deionized water (14 ml) solution. Place the flask at room temperature for two hours. Afterwards, the mixture was transferred to a dry evaporator using a rotor evaporator (bath temperature 8 (TC). The resulting material was air dried overnight at 120 C, followed by calcination at 5 ° C for 6 hours. Then according to the above example The procedure described in 1 'uses all (light yellow) Si〇2_w〇3 material for platinum/tin metal impregnation, but uses 0.6711 g (1/73 mmol) of Pt(NH3)4(N〇3)2 And 〇.41〇4 g (I.73 mmol) of tin acetate. Yield: 12.10 g of dark gray 丨 / 16 inch of extruded body. Suitable with Example I4 - 氤 氤 藉 藉 藉The gas phase chromatography (GC) of the product was tested in Examples 1-13 to determine the selectivity and yield of ethanol, as shown in Table 4. Evaporation of the acetic acid reactant feed solution, and Hydrogen and helium as carrier gases were added to the reactor together, and the combined average hourly gas space velocity (GHSV), temperature and pressure are listed in Table 4. The molar ratio of acetic acid to hydrogen in the feed stream is shown in Table 4. Gas chromatograph analysis product (crude ethanol composition) with a flame ionization detector (FID) and two thermal conductivity detectors (TCDS) The three-channel small gas chromatography 33 201121651 instrument analyzes the reactants and products. The front channel is equipped with a FID (flame ionization detector) and a CP-Sil5 (20 m) + WaxFFap (5 m) cylinder For quantification: acetaldehyde, ethanol, acetone, methyl acetate, vinyl acetate, ethyl acetate, acetic acid, ethylene glycol diacetate, ethylene glycol, ethylidene diacetate and paraldehyde. The channel is equipped with a TCD (thermal conductivity detector) and a PorabondQ cylinder for quantification: carbon dioxide, ethylene and ethane. The back channel is equipped with a TCD and Molsieve 5A cylinder and is quantified: helium, hydrogen, nitrogen, ax and carbon monoxide. Prior to the reaction, the residence time of each compound is determined by a different component tracer, and the gas chromatograph is calibrated with a calibration gas of known composition or a liquid solution of known composition. In this way, the reaction factors of the various components can be determined. 34 201121651

·< 選擇率（％) 乙醇 本發明 (N C\ s 00 oo 00 n 00 5 CN (N 一 v〇 r- 醋酸乙酯 oo o 卜 OO (N CO in (N 醋酸轉化率 (%) 5 o CM CN (N 00 CN CN 00 CO Ο (N 二 C^i 卜 反應條件 GHSV (/小時） 2500 2500 2500 6570 6570 6570 6570 2500 6570 6570 6570 6570 2500 6570 6570 6570 溫度 (°C) 250 250 250 250 250 275 250 (N 252 to CN 254 255 256 257 258 259 壓力 (仟帕） 2200 2200 1400 1400 1400 1400 1400 2200 1400 1400 1400 1400 2200 1 1400 1400 1400 氫：醋酸比例 Cri 10:1 寸 liO 寸 OO On o 5 觸媒 1 1 Si02-CaSi03(5)-Pt(3)-Sn( 1.8) KA160-CaSiO3(8)-Pt(3)-Sn(1.8) Si〇2-CaSiO3(2.5)-Pt(1.5)-Sn(0.9) Si02 + MgSi03-Pt(l .0)-Sn( 1.0) Si02-CaSi03(5)-Re(4.5)-Pd(l) Si02-Zn0(5)-Pt(l)-Sn(l) Ti02-CaSi03(5)-Pt(3)-Sn(l .8) Sn(0_5) on Si〇2 Pt(2)-Sn(2) on Si02 Pt(2)-Sn(2) on Si02 Pt(2)-Sn(2) on Si02 Pt(2)-Sn(2) on Si02 KA160-Pt(3)-Sn(1.8) Si02-Sn02(5)-Pt(l)-Zn(l) SiO2-TiO2(10)-Pt(3)-Sn(1.8) SiO2-WO3(10)-Pt(3)-Sn(1.8) 1 觸媒製備例 (N cn 寸 卜 oo ON ON o 二 CN 201121651 實施例15 -觸媒穩定性（μ ,j、時） 使氣化醋酸和氫都通過本發明氫化觸媒，該觸媒包括3重量始％，15 重里％錫和5重量％CaSi〇3，後者作為高純度高表面積(具有面積約 25〇平方米/克)二氧化石夕的促進劑，在氫對醋酸摩爾比約$ :丨（進料 速度為0.09克/分鐘的醋酸’ 16〇標準狀態立方厘米氫氣/分鐘；6〇 標準狀態立方厘米氮氣/分鐘），於溫度約225，壓力為镑/ 平方英寸(計示）（約觸千帕-計示）和GHSV = 6,570/小時之條件下 進行反應。二氧切以5% CaSiC)3穩定化。藉由固定床連續反應器系 統研究ft酸氫化’採取典型的操作條件細，帛2 5毫升固態觸媒 (M/3〇網網目，稀釋1:1體積/體積，石英片，刚酬目），在 225t進行15個小__，通過氫化及聽反應，主要生產乙醇， 乙gal乙S日。第3A圖說明觸媒選擇率，第犯圖說明產率，在 觸媒壽卩的最初。卩分，其為在反應流時間的函數。這個例子的結果如 f 3A和3B圖所示，可以重視的是能實現9〇%以上的選擇率和超過 每公斤觸媒每小時500克乙醇的產率。 宜與例Μ 性（韶過inn 2 CaSi〇3(5)-pt(3)_Sn(1 s)觸媒穩定性：在惶溫⑵此）進行超過 寺的反應’ δ平估叫心吨⑶也⑶鄉A)觸媒的性能和最 奴心定^在1〇〇小時的總反應時間觀察到觸媒的性能和選擇率只有 似乎是唯—的副產物，其漠度（〜3 _)在實驗 =纽保持不變。第4八和4B圖提供觸媒的 ί使用例16的步驟。第5Α及5Β圖顯示在觸 Γ= 觸媒的產率和選擇率作為在反應流時間的函 數。這個例子的結果如第5八和5Β圖 下，90%以上的選擇率和細 疋在此/皿度 仍有可能實現。 …母4觸媒每小時_克乙醇的產率 36 201121651 實施例18 製備實施例3的觸媒，但採取不同用量的讀體改性劑杨&，而·< Selectivity (%) Ethanol This invention (NC\ s 00 oo 00 n 00 5 CN (N-v〇r-ethyl acetate oo o OO (N CO in (N acetic acid conversion rate (%) 5 o CM CN (N 00 CN CN 00 CO Ο (N 2 C ^ i Bu reaction conditions GHSV (/hour) 2500 2500 2500 6570 6570 6570 6570 2500 6570 6570 6570 6570 2500 6570 6570 6570 Temperature (°C) 250 250 250 250 250 275 250 (N 252 to CN 254 255 256 257 258 259 Pressure (仟帕) 2200 2200 1400 1400 1400 1400 1400 2200 1400 1400 1400 1400 2200 1 1400 1400 1400 Hydrogen: Acetic acid ratio Cri 10:1 inch liO inch OO On o 5 Catalyst 1 1 SiO 2 -CaSi03(5)-Pt(3)-Sn( 1.8) KA160-CaSiO3(8)-Pt(3)-Sn(1.8) Si〇2-CaSiO3(2.5)-Pt(1.5)- Sn(0.9) SiO 2 + MgSi03-Pt(l .0)-Sn( 1.0) SiO 2 -CaSi03(5)-Re(4.5)-Pd(l) SiO 2 -Zn0(5)-Pt(l)-Sn(l Ti02-CaSi03(5)-Pt(3)-Sn(l.8) Sn(0_5) on Si〇2 Pt(2)-Sn(2) on Si02 Pt(2)-Sn(2) on Si02 Pt (2)-Sn(2) on Si02 Pt(2)-Sn(2) on Si02 KA160-Pt(3)-Sn(1.8) Si02-Sn02(5)-Pt(l)-Zn(l) SiO2- TiO2(10)-Pt(3)-Sn(1.8) SiO2-WO3(10)-Pt(3)-Sn(1.8) 1 Catalyst Preparation Example ( N cn 寸 oo ON ON o 2 CN 201121651 Example 15 - Catalyst stability (μ, j, hour) Both vaporized acetic acid and hydrogen are passed through the hydrogenation catalyst of the present invention, the catalyst comprising 3% by weight, 15 3% by weight of tin and 5% by weight of CaSi〇3, the latter as a promoter of high purity and high surface area (having an area of about 25 〇m 2 /g) of cerium oxide, in a hydrogen to acetic acid molar ratio of about $: 丨 (feeding speed) It is 0.09 g/min of acetic acid '16 〇 standard state cubic centimeter hydrogen/min; 6 〇 standard state cubic centimeter nitrogen/min), at a temperature of about 225, and the pressure is pounds per square inch (measured) (about kPa) The reaction was carried out under conditions of GHSV = 6,570 / hour. Dioxotomy was stabilized with 5% CaSiC)3. Studying the hydrogenation of ft acid by a fixed-bed continuous reactor system' takes typical operating conditions fine, 帛25 ml of solid-state catalyst (M/3 〇 mesh, diluted 1:1 volume/volume, quartz plate, just repaid) 15 small __ at 225t, mainly through the hydrogenation and audition reaction, the production of ethanol, B gal B. Figure 3A illustrates the catalyst selectivity, and the first plot illustrates the yield, at the beginning of the catalyst lifetime. The fraction is a function of the reaction time. The results of this example are shown in Figures f 3A and 3B, and it is important to achieve a selectivity of more than 9% and a yield of more than 500 grams of ethanol per kilogram of catalyst per hour. It is advisable to use the inn 2 CaSi〇3(5)-pt(3)_Sn(1 s) catalyst stability: in the temperature (2) this is carried out over the temple's response' δ flat estimate called the heart (3) (3) Township A) Catalyst performance and the most sinfulness of the catalyst. The performance and selectivity of the catalyst were observed to be only a by-product of the total reaction time of 1 hour, and its indifference (~3 _) In experiment = neon remains unchanged. Figures 4 and 4B provide the steps for using the catalyst ί. Figures 5 and 5 show the yield and selectivity of the contact = catalyst as a function of reaction time. The results of this example are shown in Figures 5 and 5, where more than 90% of the selectivity and fineness are still possible. ...male 4 catalyst per hour gram of ethanol yield 36 201121651 Example 18 The catalyst of Example 3 was prepared, but with different amounts of the read modifier Yang &

SiO2-Pt(l.5)-Sn(0.9); (ϋ) Si02-CaSi03(2.5)-Pt(1.5)-Sn (0.9); (iii) SiO2-CaSi〇3(5.0)-Pt(1.5)-Sn(0.9); (iv) Si02-CaSi〇3(7.5)-Pt (1.5)-Sn(0.9)^(v) SiO2-CaSiO3(10)-Pt(1.5)-Sn(0.9) 〇 25〇〇c 和275t及類似條件下用於醋酸氫化，亦即應巴爾（2〇〇碎/平方 英寸-計示），郎麵為2，湖、時和1G :丨絲_糊投料比， ⑽標準狀態立方厘米氫氣/分鐘對q.183克醋酸/分鐘> 轉化率如 第6A圖.所示，產率顯示於第6B圖；在職選擇率顯示於第^圖， 和在275°C選擇率顯示於第6D圖。 如第6A圖所示’在CaSi〇3用量大於2视時，竟然於μ叱和2坑 醋酸轉化率增加。而在CaSi〇3用量Q至2 5重量％時，最初的轉化 率下降，原預計CaSi〇3用量更多，將減少轉化率。但是支撐體改性 劑力:入後’令人驚賴是這種趨勢仍簡。提高轉化率也導致產率的 提问，如第6B圖所不。在第6C圖顯示支擇體改性劑增加，則選擇 率略有增加。 雖然本發明轉細描述，但在本㈣精義和顧内之各種修改對此領 域之熟悉技藝者㈣_峰社討論相_知識和技術文獻的背 景及坪細訓，其中揭露均可在此納人參考。此外，還應該認識到本 發明層面和各實施方案的部分和以下各雜色和/或所附申請專利範 圍，是可以合併或互換全部或部分。在前面各種實施方案的描述中， 提到的另-種實施方时喊當結合其他實施方案，對此領域之孰悉 技，者將能鱗^再者，那些知悉f通的技術文獻者都日肠前面描述 只是擧例說明，不是為了限制本發明範圍。 【圖式簡單說明】 以下參考各觀式雜職本發明，射_讀字係同的元件。 37 201121651 第1A圖顯示使用Si02-Pt Sn & 第出圖显頁干第Α圖觸Γ媒對乙醇和醋酸乙醋的選擇率； 不第1Α圖觸媒的乙醇和醋酸乙自旨的產率； 第1。圖顯示第1A圖觸媒的醋酸轉化率； 第2B 使用Sl〇2如氣觸媒對乙醇和醋酸6§旨的選擇率； 弟2C圖顯示第2A圖觸媒的醋酸轉化率； 第从圖顯示觸媒在15小時的測試之乙醇產率； 第3B _示第3A圖觸媒對乙醇的選擇率； 產率；SU不依據另-本發明實施方案測試超過刚小時觸媒的乙醇 第4B圖顯示第4A圖觸媒對乙醇之選擇率； =_稽另-她細軸_則、軸的乙醇 第5B圖顯示第5A圖觸媒對乙醇之選擇率； 第6A圖顯示實施例18觸媒的轉化率； 第6B圖顯示實施例18觸媒的產率； 第6C圖顯示實施例18觸媒在25(rc的選擇率；及 第6D圖顯示實施例18觸媒在275〇c的選擇率。 【主要元件符號說明】 〇 »»»> 38SiO2-Pt(l.5)-Sn(0.9); (ϋ) Si02-CaSi03(2.5)-Pt(1.5)-Sn (0.9); (iii) SiO2-CaSi〇3(5.0)-Pt(1.5) -Sn(0.9); (iv) Si02-CaSi〇3(7.5)-Pt (1.5)-Sn(0.9)^(v) SiO2-CaSiO3(10)-Pt(1.5)-Sn(0.9) 〇25〇 〇c and 275t and similar conditions for the hydrogenation of acetic acid, that is, should be Bal (2 mash / square inch - meter), Lang face is 2, lake, hour and 1G: silk wire _ paste feed ratio, (10) standard State cubic centimeters of hydrogen per minute versus q.183 grams of acetic acid per minute> The conversion is shown in Figure 6A. The yield is shown in Figure 6B; the on-the-job selectivity is shown in Figure 2, and the selectivity is at 275 °C. Shown in Figure 6D. As shown in Fig. 6A, when the amount of CaSi〇3 is more than 2, the conversion of acetic acid in μ叱 and 2 pits is increased. When the amount of CaSi〇3 is from Q to 25 wt%, the initial conversion rate is lowered, and the amount of CaSi〇3 is expected to be more, which will reduce the conversion rate. But the support modifier force: after the incident, it is surprising that this trend is still simple. Increasing conversion rates also leads to questions about yields, as shown in Figure 6B. In Figure 6C, which shows an increase in the bulk modifier, the selectivity is slightly increased. Although the present invention has been described in detail, in the context of this (4) succinct and various modifications to the field, the skilled artisan (4) _ Fengshe discussion phase _ knowledge and technical literature background and pings training, which can be disclosed here People reference. In addition, it should be understood that portions of the present invention and various embodiments and the following variegated colors and/or the scope of the appended claims may be combined or interchanged in whole or in part. In the description of the various embodiments above, the other implementations mentioned are combined with other implementations, and those skilled in the art will be able to reconcile those who are familiar with the technical literature. The foregoing description of the intestine is for illustrative purposes only and is not intended to limit the scope of the invention. [Simple Description of the Drawings] The following is a reference to the various aspects of the present invention, and the elements of the same type are the same. 37 201121651 Figure 1A shows the selectivity of ethanol and acetic acid acetate using the SiO2-Pt Sn &Rate; number 1. The figure shows the acetic acid conversion rate of the catalyst in the first layer AA; the second is the selectivity of the solvent and the acetic acid in the case of the second catalyst; the 2C diagram shows the acetic acid conversion rate of the catalyst in the second embodiment; Shows the ethanol yield of the catalyst tested at 15 hours; 3B_ shows the selectivity of the catalyst to ethanol in Figure 3A; yield; SU does not test the ethanol over the just-hour catalyst according to the other embodiment of the invention. The graph shows the selectivity of the catalyst to ethanol in Fig. 4A; = _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Conversion rate of the medium; Figure 6B shows the yield of the catalyst of Example 18; Figure 6C shows the selectivity of the catalyst of Example 18 at 25 (rc; and Figure 6D shows the catalyst of Example 18 at 275 °C Selection rate [Description of main component symbols] 〇»»»> 38

Claims (1)

201121651 七、申請專利範圍： 1. 一種觸媒，包括第一金屬，含矽支撐體，及至少一種偏矽酸鹽支 撐體改性劑。 2·如申凊專利範圍第I項所述之觸媒’其中至少有一偏矽酸鹽支撐 體改性劑選自包括(i)鹼土金屬偏矽酸鹽，（ii)鹼金屬偏矽酸鹽，（iii) 元素週期表IIB族金屬偏矽酸鹽，（iv)元素週期表ΠΙΒ族金屬偏矽 酸鹽’及其混合物之群組。 3. 如申請專利範圍第1項所述之觸媒’其中第一金屬選自包含銅， 鐵，鈷，鎳，釕，錢，把，餓，銀，鉑，鈦，辞，鉻，銖，鉬及 鎢之群組。 4. 如申請專利範圍第1項所述之觸媒，其中第一金屬用量佔觸媒總 重量的0.1至25重量％。 5. 如申請專利範圍第1項所述之觸媒，其中至少有一偏矽酸鹽支撐 體改性劑選自包含鈉，鉀，鎂，銃，釔和鋅之群組的金屬之偏矽 酸鹽。 6. 如申請專利範圍第1項所述之觸媒，其中至少有一偏矽酸鹽支撐 體改性劑係CaSi03。 7. 如申請專利範圍第1項所述之觸媒，其中至少有一偏矽酸鹽支撐 體改性劑用量為觸媒總重量的〇.1重量％至50重量％。 8. 如申請專利範圍第1項所述之觸媒，其中含矽支撐體為觸媒總重 量的25重量％至99重量％。 9. 如申請專利範圍第1項所述之觸媒，其中含矽支撐體的表面積從 50平方米/克至600平方米/克。 10. 如申請專利範圍第1項所述之觸媒，其中含矽支撐體選自包含二 氧化碎，二氧化ί夕/氧化铭，偏碎酸釣’熱解二氧化碎’高純度二 氧化矽及其混合物之群組。 39 201121651 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 如申明專利範圍第項所述之觸媒，其中含石夕支樓體包含小於1 重量％的紹’該該百分率係對觸媒總重量而言。 如申凊專利範圍第1項所述之觸媒，其中第一金屬選自包含週期 表 ΙΒ，ΠΒ，IIIB，IVB，VB，VIB，VIIB 或 VIII 族過渡金屬，鑭系金 屬，荆系金屬之群組或任一選自包含IIIA，IVA，VA或VIA族金屬 之群組。 如申請專利範圍第12項所述之觸媒，還包括不同於第—金屬之第 二金屬。 如申請專利範圍第13項所述之觸媒，其中第一金屬係鉑，而第二 金屬係錫。 如申睛專利範圍第14項所述之觸媒，其中鉑對錫之摩爾比是從 0.4 : 0.6 至 0.6 : 0.4。 如申請專利範圍第13項所述之觸媒，其中第—金屬触，而第二 金屬係銖。 如申請專利範圍第16項所述之觸媒，其中銖對鈀摩爾比為〇7 : 0.3 至 0.85 : 0.15。 如申請專利範圍第13項所述之觸媒，其中第二金屬選自包含銅， 鉬’錫，鉻，鐵’鈷，釩’鎢’鈀’鉑，鑭，鈽，錳，釕，銖， 金及鎳之群組。 如申晴專利細第η項所述之觸，其巾第二金屬用量為觸媒總 重量的0.1至10重量％。 如申請專利範圍第D項所述之觸媒，其中還包括不同於第一金屬 和第二金屬之第三金屬。 如申請專利範圍第20項所述之觸媒，其中第三金屬選自包含钻， 把，釕，銅，鋅，鉑，錫及銖之群組。 201121651 22. 如申請專利範圍第20項所述之觸媒，其中第三金屬用量為觸媒總 重量的0.05至4重量％。 23. 如申請專利範圍第1項所述之觸媒，其中觸媒適合作為氫化觸媒， 用於醋酸轉化為乙醇，而且醋酸轉化率至少10%。 24. 如申請專利範圍第23項所述之觸媒，其中該觸媒對乙醇之選擇率 至少80%。 25. 如申請專利範圍第24項所述之觸媒，其中該觸媒對曱烷，乙烷及 二氧化碳之選擇率小於4%。 26. 如申請專利範圍第1項所述之觸媒，其中該觸媒每100個小時的 使用，其產率跌幅小於6%。 27. —種滿足下式之觸媒： PtvPdwRexSnyCapS iqOr, 式中： (i) v : y比例在3 : 2和2 : 3之間，和/或(ii) w : X比例在1 : 3和 1 : 5之間；及選擇p和q，使得p : q是從1 : 20到1 : 200，與 選擇r值，以滿足價態要求；並選擇v和w，使得： 0.005 < (3·2—<0.05. q 28. 如申請專利範圍第27項所述之觸媒，其中v : y比例在3 : 2和2 : 3 之間。 29. 如申請專利範圍第27項所述之觸媒，其中w : X比例在1 : 3和1 : 5 之間。 30. —種滿足下式之觸媒： PtvPdwRexSnyAlzCapSiqOr, 式中： 41 201121651 31. 32. 33. 34. 35. 36. (i) v . y比例在3 _ 2和2 . 3之間，和/或⑼w : χ比例在i : 3和 1 : 5之間；及控制pAz和能和舞原子之相對位置，麟在表面 的布朗斯特酸基被支獅改_平衡；和選擇p和q，使得p : q 是從1 . 2G到i : 2GG ’與選擇!值，以滿足價態要求；並選擇v 和w，使得： 0.005 < (3·25Λ+Ι^) <〇〇5 q 如申明專利範圍第3〇項所述之觸媒，其中v : y比例在3 : 2和2 : 3 之間。 如申請專利範圍第30項所述之觸媒，其中w : χ比例在！ ： 3和丄：5 之間。 如申請專利範圍第30項所述之觸媒，其中至少有一種支撐體改性 劑選自包括(i)鹼土金屬氧化物，（ii)鹼金屬氧化物，（iii)鹼土金 屬偏石夕酸鹽’（iv)鹼金屬偏矽酸鹽，（v) IIB族金屬氧化物，（Vi) ΠΒ 族金屬偏矽酸鹽，（νϋ) IIIB族金屬氧化物，（viii) mB族金屬偏矽 酸鹽，及其混合物之群組。 一種觸媒，包括第一金屬，第二金屬，含矽支撐體，並在至少一 個種支撐體改性劑，其中第一金屬選自包含括銅，鐵，鈷，鎳， 釕，錢，纪，餓，銀，鉑，鈦，鋅，鉻，銖，鉬及鶴之群組，第 二金屬選自包含銅，鉬，錫，鉻’鐵’鈷，釩，鎢，鈀，鉑，鑭， 鈽，錳’銶及鎳之群組，但第二金屬不同於第—金屬。 如申請專利範圍第34項所述之觸媒，其中至少一支撐體改性劑選 自包括(1)鹼土金屬偏矽酸鹽，（H)鹼金屬偏矽酸鹽，（iii)IIB族金 屬偏石夕酸鹽’（iv)iiro族金屬偏矽酸鹽，及其混合物之群組。 如申請專利範圍第34項所述之觸媒，其中第一金屬用量為觸媒總 重量的0.1至25重量％。 42 201121651 37. 如申請專利範圍第34項所述之觸媒，其中至少有一支撐體改性劑 k自包合納’卸’鎂’銳，紀和辞之群組的金屬之偏石夕酸鹽。 38. 如申凊專利範圍帛34項所述之觸媒，其中至少有一支擇體改性劑 係 CaSi〇3。 39. ^申請專利範圍冑34摘述之觸媒，其中至少有一支撐體改性劑 疋用量為觸媒總重量的0.1重量％至50重量％。 40. 如申請專利範圍第34項所述之觸媒，其中含矽支撐體用量為觸媒 總重量的25重量％至99重量％。 41. 如申請專利範圍第34項所述之觸媒，其中含矽支撐體的表面積從 5〇平方米/克至600平方米/克。 42. 如申請專利範圍第34項所述之觸媒，其中含矽支撐體選自包含二 氧化矽，二氧化矽/氧化鋁，偏矽酸鈣，熱解二氧化矽，高純度二 氧化矽及其混合物之群組。 43，如申清專利範圍第似項所述之觸媒，其中含矽支撐體的鋁含量小 於觸媒總重量的1%。 44.如申請專利範圍第34項所述之觸媒，其中第-金屬係始，而第二 金屬係錫。 士申"月專利範圍第44項所述之觸媒，其中鉑對錫摩爾比從〇·4 : 0.6 至 0.6 : 〇 4。 46. 如申請專利範圍第34項所述之觸媒’其中第-金屬係叙，而第二 金屬係鍊。 47. 如申請專利範圍第46項所述之觸媒，其中鍊對把摩爾比是從〇·7 : 0·3 至 0.85 : 0.15。 48. 如=請專利範圍第％項所述之觸媒，其中第二金屬用量為觸媒總 重量的0.1至10重量％。 43 201121651 奶.如申請專利範圍第％項所述之觸媒，還包括不同於從第一金屬和 第二金屬之第三金屬。 见如申請專利範圍第49項所述之觸媒，其中第三金屬選自包含銘， 1巴，釘，銅，鋅，始，锡及銖。 儿如申請專利範圍第49項所述之觸媒，其中第三金屬用量為觸媒總 重量的0.05至4重量％。 52. 如申請專利範圍第％項所述之觸媒，其中該觸媒適合作為氮化觸 媒’用於醋酸轉化為乙醇，且醋酸轉化率至少聰。 53. 如巾#專她圍第52項所述之觸媒，其巾該觸騎乙醇 少 80%。 54. 如申請專利範圍第53項所述之觸媒，其中該觸騎甲烧，乙院及 -一氧化碳之選擇率小於4%。 55. 如申請專利範圍第53項所述之觸媒，其中該觸媒每⑽個小時的 使用，產率跌幅小於6%。 56. —種觸媒的製程，其步驟包括： (a)使第一金屬前體接觸到改質後的含矽支撐體，形成浸潰支撐 體’其中改質切支#體包括切材料和至少__酸鹽支擇 體改性劑;及 & 牙 0)在月bHit原第-金4的條件下，加熱浸潰支撐體以形成觸 媒。 57. 如申請專利範圍第56項所述之製程，進一步的步驟包括： (c) 使至少一偏矽酸鹽支撐體改性劑或其前體接觸含矽材料，而步 成改性支撐體前體； V (d) 在能有效形成改性支禮體條件下，加熱改性支撐體前體，而开^ 成改性支撐體。 / 201121651 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 如申明專利範圍第56項所述之製程，其中在至少部分還原氣氛 下，進行加熱。 如申明專概圍第56項所述之製程，還包括麟雜燒步驟。 如申印專利fe圍第56項所述之製程，其中至少有__偏石辩鹽支樓 體改性劑選自包括(i)驗土金屬偏石夕酸鹽，⑼齡屬偏石夕酸鹽， (叫IIB族金屬偏發酸鹽’（iv) IIffi族金屬偏矽酸鹽，及其混合物 之群組。 如申6月專利㈣第56項所述之製程，其中第—金屬選自包含鋼， 裁钻轉、釕，錢，|巴，餓，銀，在白，欽，辞，絡，鍊，在目及 鎢之群組。 如^專利姻第56項所述之製程，其中觸媒包括第—金屬，其 用量為觸媒總重量的0.1至25重量％。 如申請專利範圍第56項所述之製程，其中至少有-偏雜鹽支撐 體改性劑選自選自包含納，卸，鎂，銃，姉鋅之群組的金屬之 偏矽酸鹽。 ==項所述之製程’其中至少有一支撑 ，其中至少有-™ 50重量％。、、’、用里為觸媒總重量的〇.1重量％至 56項所述之製程，其中改質後的切支標體是 子、觸媒中，其用量為觸_ 如申請專利範圍第56項所述^ : = 士 平方米/克至_平方米/克。n3夕材抖的表面積從5〇 45 201121651 68. 如申請專利範圍第56項所述之製程，其中含矽材料選自包含二氧 化矽’二氧化矽/氧化鋁，偏矽酸鈣，熱解二氧化矽，高純度二氧 化矽及其混合物之群組。 69. 如申請專利範圍第68項所述之製程，其中含矽材料之含鋁量小於 觸媒總重量之1%。 70_如申請專利範圍第56項所述之製程，其中第一金屬選自包含週期 表ΙΒ，ΙΙΒ，ΙΠΒ，IVB，VB，VIB, VIIB或VIII族過渡金屬，鑭系金屬 之群組，婀系金屬或任一選自包含IIIA，IVA, VA或VIA族金屬之 .群組。 一金屬的第二金屬的步驟。 71.如申請專利範圍第％項所述之製程，還包括在步驟(a)和(b)之前， 之後或同時，使第二金属雜浸潰切體，及縣成為不同於第 金屬係錫。 72.如申請專利範圍帛71項所述之製程，其中第一金屬係翻，而第 其中觸媒中鉑對錫摩爾比是 其中第一金屬係I巴，而第二 其中觸媒中銖對對鈀摩爾比 其中第二金屬觸媒用量為觸 73.如申請專利範圍第72項所述之製裎， 〇·4 : 0.6 至 〇.6 : 〇_4。 74.如申請專利範圍第乃項所述之製程， 金屬係銖。 75.如申請專利範圍第74項所述之製程， 是從 0.7 : 〇.3 至 0.85 : 0.15。 其中第二金屬選自包含鋼， 麵，綱’鈽，猛，旬·，銖， 76.如申請專利範圍第71項所述之製種， 鉬’錫’絡，鐵，鈷，釩，鎢，雀巴， 金及鎳之群組。 77·如申請專利範圍第71項所述之製程， 媒總重量的0.1至10重量％。 46 201121651 78. 79. 80. 81. 82. 83. 84. 如申請專利範圍第7丨_述之製程，還包括在步驟⑷和⑼之前， 之後或同時，使不同於第—金屬和第二金屬的第三金屬前體浸潰 支撐體，及還原的步驟。 如申請專利範圍第78項所述之製程，其中第三金屬選自包含結， 鈀，釕，銅，鋅，鉑，錫及銖之群組。 如申，專利範圍第78項所述之製程，其中第三金屬存在觸媒中， 其用量為觸媒總重量的0·05至4重量％。 一種觸媒的製程，其步驟包括 (&)使第—金屬前體接觸到改質後的含矽支撐體，該支撐體包括至 少-支撐體改性劑，其中第一金屬選自包含銅，鐵，鈷，鎳， 釕’铑’鈀，餓，銥，鉑，鈦，鋅，鉻，銖，鉬及鎢之群組; (b)使不同於第一金屬之第二金屬前體接觸到改質後的含石夕支樓 體，該第二金屬選自包含銅，翻，錫，絡，鐵，結，奴，嫣， 1巴’麵’鑭，鈽，錳，銖及鎳之群組，及 (C)在能有效還原第一金屬和第二金屬的條件下，加熱改質含矽支 撐體’而形成金屬觸媒。 如申明專利範圍第81項所述之製程，其中在步驟(a)和⑻之後加 熱。 如申請專利範@第81項所述之製程，其巾在步驟(a)和⑹之間加 熱，以還原第一金屬。 如申請專利範圍第81項所述之製程，進一步的步驟包括： (d)使至少—偏矽酸鹽支撐體改性劑或其前體接觸含矽材料，形成 改質支撐體前體；及 ⑷在能有效的改質含石夕支樓體的條件下，加熱改質支樓體前體， 而形成改質含矽支撐體。 47 201121651 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 如申請專概圍第81賴述之―，射在至少部分還原氣氛下 進行加熱。 如申請專利綱第81項所述之製程，其中進—步的步驟包括： (d)煅燒觸媒。 如申請專利範圍第86項所述之製程，其中在步驟⑷和⑼後進行煅 燒。 如申請專利範圍第86項所述之製程，其中在步驟⑷和⑼之間，及 步驟⑻和(b)後，進行煅燒。 如申請專利範圍第81項所述之製程，其中至少有―支龍改性劑 選自包括(1)驗土金屬偏矽酸鹽，⑼鹼金屬偏矽酸鹽，⑽週期 表ΠΒ族金屬偏矽酸鹽，（iv)週期表ΠΙΒ族金屬偏矽酸鹽，及其 混合物之群組。 如申請專利範圍第81項所述之製程，其中第一金屬用量為觸媒總 重：£的0.1至25重量％。 如申請專利範圍第81項所述之製程，其中至少有支撐體改性劑選 自選自包含鈉，鉀，鎂，銃，釔和鋅之群組的金屬之偏矽酸鹽。 如申請專利範圍第81項所述之製程，其中至少有一支撐體改性劑 係 CaSi03。 如申請專利範圍第81項所述之製程，其中至少有一支撐體改性劑 的用量為觸媒總重量的0.1 %至50重量％。 如申請專利範圍第81項所述之製程，其中改質後的含矽支撐體用 量為觸媒總重量的25%至99重量％。 如申請專利範圍第81項所述之製程，其中改質後的含矽支撐體之 表面積從50平方米/克至600平方米/克。 48 201121651 96. 如申請專利範圍第81項所述之製程’其中改質含矽支撐體包括支 撐體材料’選自包含二氧化石夕，二氧化石夕/氧化紹，偏石夕酸舞，熱 解二氧化矽，高純度二氧化矽及其混合物之群組。 97. 如申請專利第96項所述之製程，其中改質後的含石夕支樓體包 含小於觸媒總重量的1%之I呂。 98. 如申請專利範圍第81項所述之製程，其中第一金屬係鈾，和第二 金屬係錫。 一 99. 如申請專利範圍帛98項所述之製程，其中崎錫摩爾比是從⑽： 〇·6 至 0.6 ’· 0,4。 ιυυ. 如申請專利範圍第8!項所述之製程，其中第—金屬係把，而第二 金屬係銖。 101.如申請專利範圍第100項所述之製程， 衣往錁對鈀摩爾比是從 0.7 : 0.3 至 0.85 : 0.15。 102·如申請專利範圍第S1項所述之製 Λ1 ，、中第—金屬用量為觸媒總 重置的0.1至10重量％。 肌如中請專利顧第8丨項所述之製程，還包括含 ^前=和還原第三金屬前體成為不同於第—金屬和 之第二金屬的步驟。 104. 如申請專利範圍第103項所述之製 t h 再〒第二金屬選自句含鈷， I巴，釕，銅，鋅，始，錫及銖之群組。。 105. 如申請專利範圍第1〇3項所述之製裎，豆 總重量的_至4%。 二金屬用量為觸媒 49201121651 VII. Patent application scope: 1. A catalyst comprising a first metal, a ruthenium-containing support, and at least one bismuth citrate support modifier. 2. The catalyst of claim 1, wherein at least one of the metasilicate support modifiers is selected from the group consisting of (i) alkaline earth metal metasilicate, (ii) alkali metal bismuth citrate (iii) a group of Group IIB metal metasilicates of the Periodic Table of the Elements, (iv) Periodic Table of the Group steroid metal bismuth phthalates, and mixtures thereof. 3. The catalyst described in claim 1 wherein the first metal is selected from the group consisting of copper, iron, cobalt, nickel, niobium, money, put, hungry, silver, platinum, titanium, rhodium, chrome, niobium, Group of molybdenum and tungsten. 4. The catalyst according to claim 1, wherein the first metal is used in an amount of from 0.1 to 25% by weight based on the total weight of the catalyst. 5. The catalyst of claim 1, wherein at least one of the bismuth citrate support modifier is selected from the group consisting of metals of the group consisting of sodium, potassium, magnesium, strontium, barium and zinc. salt. 6. The catalyst of claim 1, wherein at least one of the metasilicate support modifier is CaSi03. 7. The catalyst according to claim 1, wherein at least one of the bismuth citrate support modifier is used in an amount of from 0.1% by weight to 50% by weight based on the total weight of the catalyst. 8. The catalyst of claim 1, wherein the ruthenium-containing support is from 25% to 99% by weight based on the total weight of the catalyst. 9. The catalyst of claim 1, wherein the surface area of the ruthenium-containing support is from 50 square meters per gram to 600 square meters per gram. 10. The catalyst according to claim 1, wherein the ruthenium-containing support is selected from the group consisting of sulphur dioxide, sulphur dioxide, oxidized sulphur, and smashed acid fishing 'pyrolysis dioxide' high purity dioxide Group of cockroaches and their mixtures. 39 201121651 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. As stated in the scope of the patent scope, the catalyst containing the Shixi branch contains less than 1% by weight. 'The percentage is based on the total weight of the catalyst. The catalyst according to claim 1, wherein the first metal is selected from the group consisting of transition metals of 周期, ΠΒ, IIIB, IVB, VB, VIB, VIIB or VIII of the periodic table, lanthanide metals, and ceramsite metals Group or any group selected from the group consisting of metals of Group IIIA, IVA, VA or VIA. The catalyst according to claim 12, further comprising a second metal different from the first metal. The catalyst of claim 13, wherein the first metal is platinum and the second metal is tin. For example, in the catalyst described in claim 14, the platinum to tin molar ratio is from 0.4:0.6 to 0.6:0.4. For example, the catalyst described in claim 13 wherein the first metal touches the second metal system. For example, the catalyst described in claim 16 wherein the molar ratio of rhodium to palladium is 〇7:0.3 to 0.85:0.15. The catalyst according to claim 13, wherein the second metal is selected from the group consisting of copper, molybdenum 'tin, chromium, iron 'cobalt, vanadium 'tungsten' palladium' platinum, rhodium, ruthenium, manganese, osmium, iridium, Group of gold and nickel. The touch of the second metal is 0.1 to 10% by weight based on the total weight of the catalyst, as described in the Shen et al. The catalyst of claim D, which further comprises a third metal different from the first metal and the second metal. The catalyst according to claim 20, wherein the third metal is selected from the group consisting of drill, pb, bismuth, copper, zinc, platinum, tin and antimony. The catalyst according to claim 20, wherein the third metal is used in an amount of 0.05 to 4% by weight based on the total weight of the catalyst. 23. The catalyst of claim 1, wherein the catalyst is suitable as a hydrogenation catalyst for the conversion of acetic acid to ethanol and the conversion of acetic acid is at least 10%. 24. The catalyst of claim 23, wherein the catalyst has a selectivity to ethanol of at least 80%. 25. The catalyst of claim 24, wherein the catalyst has a selectivity to decane, ethane and carbon dioxide of less than 4%. 26. For the catalyst described in claim 1, wherein the catalyst decreases by less than 6% every 100 hours. 27. A catalyst that satisfies the following formula: PtvPdwRexSnyCapS iqOr, where: (i) v: y ratio is between 3:2 and 2:3, and/or (ii) w: X ratio is 1:3 and Between 1 : 5; and select p and q such that p : q is from 1: 20 to 1: 200, and select r value to meet the valence requirement; and select v and w, so that: 0.005 < (3 · 2—<0.05. q 28. The catalyst according to claim 27, wherein the ratio of v: y is between 3:2 and 2: 3. 29. As described in claim 27 Catalyst, wherein w: X ratio is between 1: 3 and 1: 5. 30. A catalyst that satisfies the following formula: PtvPdwRexSnyAlzCapSiqOr, where: 41 201121651 31. 32. 33. 34. 35. (i) v. y ratio between 3 _ 2 and 2.3, and / or (9) w : χ ratio between i: 3 and 1: 5; and control the relative position of pAz and energy and dance atoms, Lin The surface of the Brnsted acid group is changed by the lion _ balance; and the choice of p and q, so that p: q is from 1. 2G to i: 2GG ' and select! value to meet the valence state requirements; and select v and w , such that: 0.005 < (3·25Λ+Ι^) <〇〇5 q The catalyst according to Item 3, wherein the ratio of v: y is between 3: 2 and 2: 3. The catalyst described in claim 30, wherein w: χ ratio is in : : 3 and 丄The catalyst according to claim 30, wherein at least one of the support modifiers is selected from the group consisting of (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, and (iii) an alkaline earth. Metal bismuth salt '(iv) alkali metal bismuth citrate, (v) Group IIB metal oxide, (Vi) lanthanide metal bismuth citrate, (νϋ) Group IIIB metal oxide, (viii) mB Group of metal bismuth citrates, and mixtures thereof. A catalyst comprising a first metal, a second metal, a ruthenium support, and at least one support modifier, wherein the first metal is selected from the group consisting of Including copper, iron, cobalt, nickel, antimony, money, Ji, hungry, silver, platinum, titanium, zinc, chromium, antimony, molybdenum and crane groups, the second metal is selected from the group consisting of copper, molybdenum, tin, chromium a group of iron 'cobalt, vanadium, tungsten, palladium, platinum, rhodium, iridium, manganese' and nickel, but the second metal is different from the first metal. The catalyst according to item 34, wherein at least one of the support modifiers is selected from the group consisting of (1) an alkaline earth metal metasilicate, (H) an alkali metal metasilicate, and (iii) a Group IIB metal bismuth salt. '(iv) Group of iiro metal bismuth citrates, and mixtures thereof. The catalyst of claim 34, wherein the first metal is used in an amount of from 0.1 to 25% by weight based on the total weight of the catalyst. 42 201121651 37. The catalyst according to claim 34, wherein at least one of the support modifiers k is self-contained with the 'unloading' magnesium' sharp, the group of the metal and the group of the metal . 38. The catalyst described in claim 34, wherein at least one of the modifiers is CaSi〇3. 39. ^ The catalyst of the patent application 胄34, wherein at least one of the support modifiers is used in an amount of from 0.1% by weight to 50% by weight based on the total weight of the catalyst. 40. The catalyst according to claim 34, wherein the ruthenium-containing support is used in an amount of from 25% by weight to 99% by weight based on the total weight of the catalyst. 41. The catalyst of claim 34, wherein the surface area of the ruthenium-containing support is from 5 square meters per gram to 600 square meters per gram. 42. The catalyst according to claim 34, wherein the ruthenium-containing support is selected from the group consisting of cerium oxide, cerium oxide/alumina, calcium metasilicate, pyrogenic cerium oxide, high purity cerium oxide. And a group of its mixtures. The catalyst according to claim 1, wherein the ruthenium-containing support has an aluminum content of less than 1% by weight based on the total weight of the catalyst. 44. The catalyst of claim 34, wherein the first metal is the first and the second metal is tin. The catalyst described in Section 44 of the patent application, in which the platinum to tin molar ratio is from 〇·4:0.6 to 0.6: 〇 4. 46. The catalyst described in claim 34, wherein the first metal is a metal and the second metal is a chain. 47. For the catalyst described in claim 46, the chain pair molar ratio is from 〇·7 : 0·3 to 0.85 : 0.15. 48. If the catalyst is in the scope of claim 1, wherein the second metal is used in an amount of 0.1 to 10% by weight based on the total weight of the catalyst. 43 201121651 Milk. The catalyst described in claim 100, further comprising a third metal different from the first metal and the second metal. See the catalyst as described in claim 49, wherein the third metal is selected from the group consisting of Ming, 1 bar, nail, copper, zinc, tin, tin and bismuth. The catalyst according to claim 49, wherein the third metal is used in an amount of 0.05 to 4% by weight based on the total weight of the catalyst. 52. The catalyst of claim 5, wherein the catalyst is suitable as a nitriding catalyst for the conversion of acetic acid to ethanol, and the conversion of acetic acid is at least Cong. 53. If the towel is specially designed for her around the 52nd item, the towel should be 80% less ethanol. 54. The catalyst according to claim 53 of the patent application, wherein the selection rate of the beating, the hospital and the carbon monoxide is less than 4%. 55. The catalyst described in claim 53 of the patent scope, wherein the catalyst decreases by less than 6% every (10) hours of use. 56. A process for a catalyst, the steps comprising: (a) contacting a first metal precursor with a modified ruthenium-containing support to form an impregnation support, wherein the modified cut support body comprises a cut material and At least __ acid salt modifier; and & tooth 0) under conditions of the month bHit original - gold 4, the impregnation support is heated to form a catalyst. 57. The process of claim 56, the further comprising: (c) contacting at least one metasilicate support modifier or precursor thereof with the cerium-containing material and forming the modified support Precursor; V (d) The modified support precursor is heated and the modified support is opened under the condition that the modified support body can be effectively formed. / 201121651 58. 59. 60. 61. 62. 63. 65. 65. 67. 67. The process of claim 56, wherein the heating is carried out under at least a partial reducing atmosphere. For example, the process described in item 56 of the general specification also includes the step of lining up. For example, the process described in the 56th paragraph of the patent application, the at least __ 偏 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Acid salt, (Group IIB metal partial acid salt) (iv) IIffi metal bismuth citrate, and a mixture thereof. For the process described in claim 56 of the June patent (4), the first metal selection Self-contained steel, cutting, turning, money, |ba, hungry, silver, in white, chin, resignation, network, chain, in the group of tungsten and tungsten. Wherein the catalyst comprises a first metal in an amount of from 0.1 to 25% by weight based on the total weight of the catalyst. The process of claim 56, wherein at least the hetero--salt support modifier is selected from the group consisting of a metal metatanning salt of the group of sodium, unloading, magnesium, antimony, and antimony. The process described in the == item has at least one support, at least - 50% by weight of TM.,, ', The total weight of the catalyst is from 11% by weight to the process described in 56 items, wherein the modified cut-off target body is in the sub-catalyst, and the amount is touched. The range of patents mentioned in item 56 is: : = square meters / gram to _ square meters / gram. The surface area of n3 eves from 5 〇 45 201121651 68. The process described in claim 56, including 矽The material is selected from the group consisting of cerium oxide 'cerium oxide/alumina, calcium metasilicate, pyrogenic cerium oxide, high purity cerium oxide and mixtures thereof. 69. As described in claim 68 The process, wherein the aluminum content of the ruthenium-containing material is less than 1% of the total weight of the catalyst. 70_ The process of claim 56, wherein the first metal is selected from the group consisting of 周期, ΙΙΒ, ΙΠΒ, IVB, a VB, VIB, VIIB or VIII transition metal, a group of lanthanide metals, a lanthanide metal or a group selected from the group consisting of metals of Groups IIIA, IVA, VA or VIA. A step of a second metal of a metal. 71. The process of claim 100, further comprising, prior to or simultaneously with steps (a) and (b), causing the second metal to be impregnated, and the county to be different from the first metal tin. 72. If the patent application scope is described in item 71, the first metal system is turned over. Wherein the platinum-to-tin molar ratio in the catalyst is the first metal system I bar, and the second one of the catalysts has a ruthenium-to-palladium molar ratio in which the second metal catalyst is used as the contact 73. The system described in the paragraph, 〇·4: 0.6 to 〇.6: 〇_4. 74. The process described in the scope of the patent application, metal system 75 75. As described in claim 74 The process is from 0.7 : 〇.3 to 0.85 : 0.15. The second metal is selected from the group consisting of steel, surface, and 钸 '钸, 猛, ··, 铢, 76. The system described in claim 71 Species, molybdenum 'tin' complex, iron, cobalt, vanadium, tungsten, sparrow, gold and nickel. 77. The process described in claim 71, wherein the total weight of the medium is from 0.1 to 10% by weight. 46 201121651 78. 79. 80. 81. 82. 83. 84. If the scope of the patent application is described in paragraph 7__, it is also included before, after or at the same time as steps (4) and (9), to make it different from the first metal and the second The third metal precursor of the metal impregnates the support, and the step of reducing. The process of claim 78, wherein the third metal is selected from the group consisting of a knot, palladium, rhodium, copper, zinc, platinum, tin and antimony. The process of claim 78, wherein the third metal is present in the catalyst in an amount of from 0.05 to 4% by weight based on the total weight of the catalyst. A catalyst process, the method comprising: (&) contacting a first metal precursor with a modified ruthenium-containing support, the support comprising at least a support modifier, wherein the first metal is selected from the group consisting of copper , iron, cobalt, nickel, 钌'铑' palladium, hungry, antimony, platinum, titanium, zinc, chromium, antimony, molybdenum and tungsten; (b) contact with a second metal precursor different from the first metal After the upgraded stone-bearing building, the second metal is selected from the group consisting of copper, turn, tin, iron, iron, knot, slave, bismuth, 1 bar 'face' 镧, 钸, manganese, strontium and nickel The group, and (C), under conditions effective to reduce the first metal and the second metal, heat the modified ruthenium-containing support to form a metal catalyst. The process of claim 81, wherein the heating is performed after steps (a) and (8). The process of applying the patent specification @第81, the towel is heated between steps (a) and (6) to reduce the first metal. For the process described in claim 81, further steps include: (d) contacting at least a bismuth citrate support modifier or a precursor thereof with a ruthenium-containing material to form a modified support precursor; (4) Under the condition that the stone building can be effectively modified, the precursor of the building body is heated and modified to form a modified supporting body. 47 201121651 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. If you apply for the special section of the 81st, the shot is heated in at least part of the reducing atmosphere. For example, the process described in claim 81, wherein the step of further comprises: (d) calcining the catalyst. The process of claim 86, wherein the calcination is carried out after steps (4) and (9). The process described in claim 86, wherein between steps (4) and (9), and after steps (8) and (b), calcination is carried out. For example, in the process described in claim 81, at least the "Dragon" modifier is selected from the group consisting of (1) soil-spectrum metal bismuth citrate, (9) alkali metal bismuth citrate, (10) periodic table bismuth metal Citrate, (iv) a group of bismuth metal bismuth citrates, and mixtures thereof. The process of claim 81, wherein the first metal is used in an amount of from 0.1 to 25% by weight of the catalyst. The process of claim 81, wherein at least one of the support modifiers is selected from the group consisting of metal metasilicates comprising the group of sodium, potassium, magnesium, strontium, barium and zinc. The process described in claim 81, wherein at least one of the support modifiers is CaSi03. The process of claim 81, wherein at least one of the support modifiers is used in an amount of from 0.1% to 50% by weight based on the total weight of the catalyst. The process of claim 81, wherein the modified ruthenium-containing support is used in an amount of from 25% to 99% by weight based on the total weight of the catalyst. For example, the process described in claim 81, wherein the modified ruthenium-containing support has a surface area of from 50 m 2 /g to 600 m 2 /g. 48 201121651 96. The process of claim 81, wherein the modified ruthenium-containing support comprises a support material selected from the group consisting of a dioxide dioxide, a sulphur dioxide, an oxidation, and a sulphuric acid dance. A group of pyrogenic cerium oxide, high purity cerium oxide and mixtures thereof. 97. The process of claim 96, wherein the modified shixi branch contains less than 1% of the total weight of the catalyst. 98. The process of claim 81, wherein the first metal is uranium and the second metal is tin. I. 99. For the process described in the scope of patent application 帛98, the molar ratio of Saki is from (10): 〇·6 to 0.6 ’· 0,4. Ιυυ. For the process described in claim 8 of the patent scope, the first metal is the metal and the second metal is the metal. 101. The process of the coating to palladium molar ratio is from 0.7:0.3 to 0.85:0.15, as described in claim 100. 102. As claimed in claim S1, the amount of metal used is 0.1 to 10% by weight of the total catalyst reset. The process of the invention, as described in the patent application, further includes the steps of: pre- and reducing the third metal precursor to be different from the first metal and the second metal. 104. The system of claim 12, wherein the second metal is selected from the group consisting of cobalt, I bar, bismuth, copper, zinc, tin, tin and antimony. . 105. _ to 4% of the total weight of the beans, as stated in Article 1-3 of the patent application. The amount of the second metal is the catalyst 49