201229013 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種二元醇_ 哔頸化合物的製造方法，发係 醛類化合物在催化劑存在下，於姓& ，、你由 一 、符弋溫度和壓力之條件ητ、# 行氫化反應，以製造二元醇類各人 進 #丄、 5物。本發明特別是關於— 種由4-經基丁越製造1 4-丁-防 、 一知的方法。 【先前技術】 1，4-丁二醇（BD0)是一種 ^ 要的有機化工原料，可生逄 四氳呋喃（THF)、p丁内酉旨f 了生產 匕笙客。， 和聚對苯二曱酸二 酉日專產叩。四氫呋喃和γ_ 丁内 化工、紡織、油墨、造紙H為溶劑廣泛應用於醫藥、 生產的聚四亞f基乙二'電鑛等行業1四氫吱喃 氨醋樹脂⑽）及彈性纖唯^MW可用於合成高性能聚 2-轉_㈣基鱗用於合成 一醇盥對田缺C： + 久、，隹生素B12的中間體。1，4_丁 一知〃對本—甲酸反應可生 PRT Η 從又對本二曱酸二丁酯（PBT)， PBT疋一種性能優良的工程 子和電器等行業。由於！4 丁 4，廣泛用於汽車、機械、電 巨大的市場發展前景，因此〜醇具有廣泛用途，並且具有 a ^ , ，越來越為人們所關注。 業上1，4-丁二醇可 λ ^ , ^ , c 错由‘羥基丁醛進行氫化反應 如擔载於金屬氧化物上 +屬於金屬擔載型催化劑’例 見的氫化催化劑。其中，以換I鎳、釕、#、始，都是常 擔載型的鎳及釕催化劑，或是雷 TF1004503 201229013 氏鎳（Raney Nickel)催化劑擁有較佳的氫化活性表現〔us 5426250〕。近年來，陸續有文獻報導經過高分子穩定化的奈 米金屬簇催化劑，例如貴金屬鉑、鈀、釕等，在氫化反應上 如烯類選擇性氫化、雙酮類選擇性氫化、不飽和醛選擇性氫 化、丙烯酸曱酯選擇性氫化等，擁有優越活性和選擇性〔201229013 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a diol-cervical compound, in which a aldehyde compound is present in the presence of a catalyst, and a surname & The conditions of temperature and pressure are ητ, # hydrogenation reaction to produce diols, each of which is #丄, 5. More particularly, the present invention relates to a method for producing 1-4-but-protected 4-pyridyl. [Prior Art] 1,4-butanediol (BD0) is a kind of organic chemical raw material, which can produce scorpion THF and THF. , and poly-terephthalic acid two-day specialties. Tetrahydrofuran and γ_ Ding Nei Chemical, textile, ink, paper H is a solvent widely used in medicine, production of polytetrazide f-based ethylene II's ore and other industries 1 tetrahydrofuran urethane resin (10)) and elastic fiber only ^ MW It can be used to synthesize high performance poly-2-trans-(tetra) basal scales for the synthesis of an alcohol oxime on the field of C: + long-term, vitamin B12 intermediates. 1,4_丁 一知〃 The reaction to the formic acid can be produced PRT Η From the dibutyl phthalate (PBT), PBT 疋 an excellent engineering and electrical industries. due to! 4 Ding 4, widely used in automotive, machinery, electricity, huge market development prospects, so ~ alcohol has a wide range of uses, and has a ^, is getting more and more people's attention. In the industry, 1,4-butanediol may be a hydrogenation catalyst of λ ^ , ^ , c which is hydrogenated by 'hydroxybutanal, such as supported on a metal oxide + a metal-supported catalyst. Among them, nickel, ruthenium catalysts, which are often supported on the basis of nickel, ruthenium, ruthenium, and ruthenium, or fluorene TF1004503 201229013 nickel (Raney Nickel) catalyst have better hydrogenation activity [us 5426250]. In recent years, there have been reports in the literature on polymer-stabilized nano-metal cluster catalysts, such as noble metals such as platinum, palladium, rhodium, etc., in hydrogenation reactions such as selective hydrogenation of olefins, selective hydrogenation of diketones, and selection of unsaturated aldehydes. Hydrogenation, selective hydrogenation of decyl acrylate, etc., with superior activity and selectivity [
Chem. Rev. 92 (1992) 1709) [Appl. Catal., A: Chem. 144 (1999) 123〕。 擔載於載體之上的金屬奈米蔟（metai nano_ciusters )為主 要的反應活性位置，其由特定數目原子組成，接近單一分散 且有序結構之金屬奈米粒子，具有異於塊狀金屬與單一金屬 原子之獨特化學與物理性質。製備金屬奈米簇或金屬奈米膠 體微粒的技術有化學還原法、電化學還原法、氣相沉積法、 微波輻射法、UV光解法、熱分解法等。其中，化學還原法 〔J. Am. Chem. Soc.，93 (1971) 1301〕因為具有容易製備、 分散穩定、粒徑較小及分布較窄的優點，在催化應用上廣被 應用。而在工業生產上，催化劑必須要有良好再現性，因此， 常於製備過程中將其負載於異相擔體上，或添加高分子、界 面活性劑、配位基當做穩定劑’並分散於溶劑中加以保存及 使用’以避免奈米微粒聚集成長〔j Mol. Catal. A，177(2001) 113.〕。 提高氫化催化劑之催化活性、增加穩定性及延長反應壽 命，為氫化催化劑研究改質之重點。本發明提供一種高穩定 TF1004503 4 201229013 性、高分散性、高活性之核-殼式氫化催化劑的製備方法 利用奈米粉體技術（nano_particle engineering)，將金屬活性 位置表面均勻鑛上一層或多層奈米級殼層。藉由這樣 殼結構（Core-shell structure )，改變中心粒子表面的電十生 功能性、活性等，使其擁有良好的分散性及穩定性。 藉由外殼的保護，減少中心金屬受到外來化學上或物理上之 影響’以延長反應壽命，並利用所生成之孔道，提高甘 勺丹反應 • 選擇性。 【發明内容】 本發明之一目的係在於提供一種高穩定性、高分散性、言 活性之核-殼式氫化催化劑的製備方法。 ° 本發明之另一目的係提供一種可用於醛類化合物氣化 應之核-殼式氫化催化劑的製備方法。 本發明之再-目的係提供—種二元醇類化合物的製造 •法’其在特別是核-殼式氣化催化劑的存在下，於特定= 和壓力下由㈣化合物進行氫化反應而製造二元醇類I； 物。 製備核-毅型式之奈米粒子，除了可將多功能結合在一起 外’也可能產生新的特性。1而言，其目標可區分為四大 項：-、修飾奈錄子的塊材特性，或產生不同於原成分之 新特|± ’ —調I奈米粒子的表面特性，以改變其表面電荷 密度、功能性、反應性、生物相容性、穩定性及分散性；三、 TF1004503 201229013 創造多功能性複合 以核。粒子為板模，製備中空球殼；四 奈米粒子。 核、"又型式之奈米粒子製備過程中，除了藉由各成分反 應、、f核、成長速率過大的差異性來產生外，最常見的製傷 方法疋以兩步驟來完成。亦即，先以_般單成分奈米粒子合 成法合成所需要的核心粒子，再進—步以披覆技術產生奈米 殼層。Chem. Rev. 92 (1992) 1709) [Appl. Catal., A: Chem. 144 (1999) 123]. The metal nano-ciusters supported on the carrier are the main reactive sites, which are composed of a specific number of atoms, close to a single dispersed and ordered structure of metal nanoparticles, which is different from the bulk metal and a single The unique chemical and physical properties of metal atoms. Techniques for preparing metal nanoclusters or metal nanocolloidal particles include chemical reduction, electrochemical reduction, vapor deposition, microwave irradiation, UV photolysis, thermal decomposition, and the like. Among them, the chemical reduction method [J. Am. Chem. Soc., 93 (1971) 1301] has been widely used in catalytic applications because of its advantages of easy preparation, stable dispersion, small particle size, and narrow distribution. In industrial production, the catalyst must have good reproducibility. Therefore, it is often loaded on a heterogeneous support during the preparation process, or a polymer, a surfactant, a ligand is added as a stabilizer and dispersed in a solvent. Save and use 'to avoid the growth of nanoparticle aggregates [j Mol. Catal. A, 177 (2001) 113.]. Increasing the catalytic activity of the hydrogenation catalyst, increasing the stability and prolonging the reaction life are the key points for the research and development of the hydrogenation catalyst. The invention provides a high stability TF1004503 4 201229013 high-dispersion, high-activity nuclear-shell hydrogenation catalyst preparation method using nano-particle engineering to uniformly ore the surface of the metal active site with one or more layers of nano Grade shell. By such a shell-shell structure, the electric function and activity of the surface of the center particle are changed, so that it has good dispersibility and stability. By protecting the outer shell, the central metal is reduced by external chemical or physical influences to extend the reaction life and utilize the generated pores to increase the selectivity of the Cao Dan. SUMMARY OF THE INVENTION One object of the present invention is to provide a method for preparing a core-shell hydrogenation catalyst having high stability, high dispersibility, and activity. Another object of the present invention is to provide a process for the preparation of a core-shell hydrogenation catalyst which can be used for the gasification of an aldehyde compound. A further object of the present invention is to provide a process for the production of a glycol compound which is produced by hydrogenation of a compound (4) under specific = and pressure in the presence of a core-shell gasification catalyst, in particular Alkaloids I; The preparation of core-type nanoparticles, in addition to combining versatility, may also yield new properties. 1 , its objectives can be divided into four major items: -, modify the characteristics of the block of the Nai Lizi, or produce a new characteristic of the original composition of the original composition of the nanoparticle to change the surface Charge density, functionality, reactivity, biocompatibility, stability and dispersion; III. TF1004503 201229013 Create a versatile composite with a core. The particles are plate molds, and a hollow spherical shell is prepared; four nano particles. In the preparation process of nuclear and "types of nanoparticles, in addition to the differences in composition reaction, f-nucleus, and excessive growth rate, the most common methods of injury are completed in two steps. That is, the core particles required are synthesized by a single-component nanoparticle synthesis method, and then the nanoshell layer is produced by a coating technique.
本發明係在催化劑存在下，由賴化合物進行氫化反應而 製造二70_貞化合物。制地，本發明係在核_殼式催化劑 的存在下，由醛類化合物製造二元醇類化合物，其中誃 殼式催化劑實驗式為： Λ X M@Si〇2 其中Μ表示活性金屬。 根據本發明之一具體例，係在核-殼式催化劑的存在下， 由4-羥基丁醛製造1，4-丁二醇。 本發明中’催化劑添加量係佔反應液總重〇丨至5重量0/〇 之範圍内，較佳為0.4至2重量％之範圍内；反應溫度介於 80至150 °C之間，較佳係介於90至130 °C之間；反應壓 力介於200至1500 psig之間’較佳係介於4〇〇至1300 psig 之間。 本發明中所使用之核-殼式催化劑，其特性與製備條件有 關，又當使用於备類虱化反應時，反應收率與所使用之活性 TF1004503 6 201229013 金屬種類與用量、反應溫度、壓力等有關。 本發明可應用於批次製程及連續式製程’包含連續攪拌反 應器（Continuous Stirred Tank Reactor，CSTR)、固定床反 應器（Packed Bed Reactor)、流體化床反應器（Fluidized Bed Reactor)等。 以下藉由具體實施例進一步說明本發明之特點與功效，但 其並非用來限制本發明之範疇。 • 【實施方式】 本說明書中所記載之轉換頻率（Turnover Frequency，TOF) 係根據下列方程式計算： TOF( 1/s)=[酸類化合物添加量_反應後搭類化合物剩餘 量](mo1)/活性金屬添加量(mol)/反應時間（Sec) Φ (比較例1) (1)氫化反應測試 將50毫升4-羥基丁醛反應液及〇·2克雷氏鎳催化劑置於 氫化反應器中’控制反應溫度為95Ϊ，以氫氣建壓至400 psig。於反應時間〇 5小時取樣，樣品以氣相層析儀分析， 其結果列於表一。 (實施例1) (1)催化劑製備 TF1004503 7 201229013 將0.0626 A氣化舒鹽類溶於3毫升去離子水，再逐來將 冋为子穩疋劑、還原劑加入，於鹼性環境下攪拌均勻， 溶解，隨後以_進行清洗，取出黑色膠體溶液並乾燥使^The present invention produces a di-70 贞 compound by hydrogenation of a lysine compound in the presence of a catalyst. In the present invention, the present invention produces a glycol compound from an aldehyde compound in the presence of a core-shell catalyst, wherein the shell catalyst is of the formula: Λ X M@Si〇2 wherein Μ represents an active metal. According to a specific embodiment of the present invention, 1,4-butanediol is produced from 4-hydroxybutanal in the presence of a core-shell catalyst. In the present invention, the amount of catalyst added is in the range of 5 to 0% by weight of the reaction liquid, preferably 0.4 to 2% by weight; and the reaction temperature is between 80 and 150 °C. The best is between 90 and 130 ° C; the reaction pressure is between 200 and 1500 psig 'better between 4 and 1300 psig. The core-shell catalyst used in the present invention has properties related to the preparation conditions, and when used in the preparation of the deuteration reaction, the reaction yield and the activity used TF1004503 6 201229013 metal type and amount, reaction temperature, pressure And so on. The present invention is applicable to batch processes and continuous processes, including a Continuous Stirred Tank Reactor (CSTR), a Packed Bed Reactor, a Fluidized Bed Reactor, and the like. The features and effects of the present invention are further illustrated by the following examples, which are not intended to limit the scope of the invention. • [Embodiment] The Turnover Frequency (TOF) described in this manual is calculated according to the following equation: TOF( 1/s) = [addition amount of acid compound _ residual amount of compound after reaction] (mo1) / Active metal addition amount (mol) / reaction time (Sec) Φ (Comparative Example 1) (1) Hydrogenation reaction test 50 ml of 4-hydroxybutanal reaction solution and 〇·2 g of Raney nickel catalyst were placed in a hydrogenation reactor 'Control reaction temperature is 95 Ϊ, with hydrogen pressure to 400 psig. Samples were taken at reaction time 〇 5 hours, and the samples were analyzed by gas chromatography. The results are shown in Table 1. (Example 1) (1) Preparation of catalyst TF1004503 7 201229013 Dissolve 0.0626 A gasified sulphate in 3 ml of deionized water, and then add hydrazine as a stabilizer and a reducing agent, and stir under alkaline conditions. Uniform, dissolved, then washed with _, remove the black colloidal solution and dry to make ^
燥完成後，將其與0.998毫升去離子水、0.339毫升氨水、L 6.643毫升乙醇均勻互溶，再加入模板劑，擾摔24小:，取 出黑色膠體溶液並乾燥，乾燥完成後，於空氣氣氛下锻燒數 小時，並於氬氣與氫氣混合氣氛下煅燒3_5小時，即得所需 之Ru@Si02催化劑。 (2)氫化反應測試 將50毫升4-羥基丁醛反應液及〇 2克Ru@Si〇2催化劑置 於鼠化反應器中，控制反應溫度為95°c，以氫氣建壓至4〇〇 psig。於反應時間〇.5小時取樣，樣品以氣相層析儀分析， 其結果列於表一。 (實施例2-5) (1)催化劑製備 將實施例1中的氯化釕鹽類以其他金屬鹽類取代，利用與 實施例1相同之觸媒製備方法製備所需之催化劑。 (2)氫化反應測試 依實施例1相同之氫化反應測試方法進行，催化劑分別改 為 Rh@Si02、Pd@Si02 ' Pt@Si02、Ni@Si02，其結果列於 表一。 TF1004503 8 201229013 表一、不同活性金屬之核-殼式催化劑的反應活性 No. 催化劑 催化劑 (wt%) 反應壓力 (psig) 反應溫度 (°C) 反應時間 (Hr) T〇F (1/s) 比較例1 雷氏鎳 實施例1 RU@Si〇2 實施例2 Rh@Si02 0.4 400 Λ C 實施例3 rpd®Si〇? 95 v. D 0 fn 1 實施例4 實施例5 Ni@Si〇2 _^----- 由表一實驗結果可知，本實驗所發明之核-殼式催化劑可 有效進行‘羥基丁醛氫化製備1，4-丁二醇反應，並較商業觸 媒雷氏鎳擁有更好的催化活性，其中，又以Ru@Si〇2、 Pd@Si〇2擁有較佳之反應活性。 (實施例6-7) (1) 催化劑製備 與實施例1相同之觸媒製備方法製備所需之催化劑。 (2) 氫化反應測試 將50毫升4-羥基丁醛反應液及〇.2克Ru@Si02催化劑置 於氫化反應器中，控制反應溫度為95°C，分別將氫氣建壓 至800、1000 psig。於反應時間0.5小時取樣，樣品以氣相 層析儀分析，其結果列於表二。 TF1004503 9 201229013 不同反應壓力下Ru@Si02的反應活性 Γ—----- 一 ~ ·一 No. 催化劑 催化劑 (wt%) 反應壓力 (psig) 反應溫度 (°C) 反應時間 (Hr) T0F (1/s) 實施例Ί~ -- _R^Si〇2 400 0.026 賞施例6 0.4 800 95 0.5 0.044 I现例7 1000 0.055 由表二實驗結果可知，隨著反應壓力之增加，Ru@Si02 的氫化活性亦隨之增加。 (實施例8-9) φ (1) 催化劑製備 與實施例1相同之觸媒製備方法製備所需之催化劑。 (2) 氫化反應測試 將50毫升4-羥基丁醛反應液及0.2克Ru@si〇2催化劑置 於氫化反應器中，控制反應溫度分別為95、110、12(TC， 將氫氣建壓至400 psig。於反應時間0.5小時取樣，樣品以 氣相層析儀分析，其結果列於表三。 · 表三不同反應溫度下Ru@Si〇2的反應活性After the completion of the drying, it is uniformly dissolved with 0.998 ml of deionized water, 0.339 ml of ammonia water, and L 6.643 ml of ethanol, and then the template is added, and the interference is broken 24 times: the black colloid solution is taken out and dried, and after drying, in an air atmosphere The calcination is carried out for several hours and calcined in a mixed atmosphere of argon and hydrogen for 3-5 hours to obtain the desired Ru@SiO 2 catalyst. (2) Hydrogenation reaction test 50 ml of 4-hydroxybutanal reaction solution and 2 g of Ru@Si〇2 catalyst were placed in a mouse reactor, and the reaction temperature was controlled to 95 ° C, and the pressure was controlled to 4 Torr with hydrogen. Psig. Samples were taken at a reaction time of 〇5 hours, and the samples were analyzed by gas chromatography, and the results are shown in Table 1. (Example 2-5) (1) Preparation of catalyst The ruthenium chloride salt of Example 1 was replaced with another metal salt, and the desired catalyst was prepared by the same catalyst preparation method as in Example 1. (2) Hydrogenation reaction test The same hydrogenation reaction test method as in Example 1 was carried out, and the catalysts were changed to Rh@Si02, Pd@Si02 'Pt@Si02, Ni@Si02, respectively, and the results are shown in Table 1. TF1004503 8 201229013 Table 1. Reactivity of core-shell catalysts of different active metals No. Catalyst catalyst (wt%) Reaction pressure (psig) Reaction temperature (°C) Reaction time (Hr) T〇F (1/s) Comparative Example 1 Rey Nickel Example 1 RU@Si〇2 Example 2 Rh@Si02 0.4 400 Λ C Example 3 rpd®Si〇? 95 v. D 0 fn 1 Example 4 Example 5 Ni@Si〇2 _^----- From the experimental results in Table 1, the core-shell catalyst invented in this experiment can effectively carry out the reaction of hydrogenation of hydroxybutyraldehyde to 1,4-butanediol, and it is more commercial than the commercial catalyst. It has better catalytic activity, among which Ru@Si〇2 and Pd@Si〇2 have better reactivity. (Example 6-7) (1) Preparation of catalyst The same catalyst preparation method as in Example 1 was carried out to prepare a desired catalyst. (2) Hydrogenation reaction test 50 ml of 4-hydroxybutanal reaction solution and 克.2 g of Ru@Si02 catalyst were placed in a hydrogenation reactor to control the reaction temperature to 95 ° C, and the hydrogen pressure was respectively set to 800, 1000 psig. . Samples were taken at a reaction time of 0.5 hours, and the samples were analyzed by gas chromatography, and the results are shown in Table 2. TF1004503 9 201229013 Reactive activity of Ru@Si02 at different reaction pressures ----- One-to-one catalyst catalyst (wt%) Reaction pressure (psig) Reaction temperature (°C) Reaction time (Hr) T0F ( 1/s) Example Ί~ -- _R^Si〇2 400 0.026 Appreciation Example 6 0.4 800 95 0.5 0.044 I Present 7 1000 0.055 From the experimental results in Table 2, as the reaction pressure increases, Ru@Si02 The hydrogenation activity also increases. (Example 8-9) φ (1) Catalyst preparation The catalyst preparation method was the same as that of Example 1, and the desired catalyst was prepared. (2) Hydrogenation reaction test 50 ml of 4-hydroxybutanal reaction solution and 0.2 g of Ru@si〇2 catalyst were placed in a hydrogenation reactor, and the reaction temperatures were controlled to be 95, 110, and 12 (TC, respectively. 400 psig. Sampled at a reaction time of 0.5 hours, the sample was analyzed by gas chromatography, and the results are shown in Table 3. Table 3 Reactivity of Ru@Si〇2 at different reaction temperatures
No. 催化劑 催化劑 (wt%) 反應壓力 (psig) 反應溫度 (°C) 反應時間 (Hr) TOF (1/s) 實施例1 Ru@Si〇2 95 0.026 實施例8 Ru@Si02 0.4 400 110 0.5 0.037 實施例9 Ru@Si〇2 120 0.049 由表三實驗結果可知，隨著反應溫度之增加，Ru@Si02 的氫化活性亦隨之增加。 TF1004503 10No. Catalyst catalyst (wt%) Reaction pressure (psig) Reaction temperature (°C) Reaction time (Hr) TOF (1/s) Example 1 Ru@Si〇2 95 0.026 Example 8 Ru@Si02 0.4 400 110 0.5 0.037 Example 9 Ru@Si〇2 120 0.049 From the results of the third experiment, it is known that as the reaction temperature increases, the hydrogenation activity of Ru@Si02 also increases. TF1004503 10