TWI539994B - Generation of polyols from saccharides and catalyst system therefor - Google Patents
Generation of polyols from saccharides and catalyst system therefor Download PDFInfo
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Description
本發明係關於觸媒系統及使用該觸媒系統自含有醣類之原料生產至少一種多元醇的製程。該製程涉及使氫、水及包含醣類之原料與觸媒系統接觸以生產包含至少一種多元醇之流出物，及自該流出物回收該多元醇。該觸媒系統包含非受載型催化組份及受載型催化組份二者。 The present invention relates to a catalyst system and a process for producing at least one polyol from a saccharide-containing material using the catalyst system. The process involves contacting hydrogen, water, and a saccharide-containing material with a catalyst system to produce an effluent comprising at least one polyol, and recovering the polyol from the effluent. The catalyst system comprises both a non-supported catalytic component and a supported catalytic component.
本申請案主張對2011年7月28日申請之美國申請案第13/192,907號及2011年7月28日申請之美國申請案第13/192,970號之優先權，其內容均以引用的方式全文併入本文中。 The present application claims priority to U.S. Application Serial No. 13/192,907, filed on Jul. 28, 2011, and Serial No. 13/192,970, filed on Jul. 28, 2011, the content of Incorporated herein.
多元醇係用於製造冷天氣流體、化妝品、聚酯及許多其他合成產品之有價值材料。自醣類而非化石燃料衍生之烯烴生產多元醇可係環境更友好且更具經濟吸引力之製程。以前，已自多羥基化合物生產多元醇，參見WO 2006/092085及US 2004/0175806。最近，在受載型碳化物觸媒上醣類至乙二醇之催化轉化係揭示於Catalysis Today,147,(2009)77-85中。US 2010/0256424、US 2010/0255983及WO 2010/060345教示自醣類製備乙二醇之方法及催化該反應之碳化鎢觸媒。在Angew.Chem.Int.Ed 2008,47,8510-8513及支持資訊及Chem.Commun.,2010,46,862-864中已公佈碳化鎢觸媒成功用於醣類至乙二醇之分批模式直接催化轉化。在ChemSusChem 2010,3,63-66中將少量鎳添加至碳化鎢觸媒中。揭示用於將纖維素直接轉化 至乙二醇或丙二醇之本技術所熟知觸媒的其他參考文獻包括WO 2010/060345；US 7,767,867；Chem.Commun.,2010,46,6935-6937；Chin.J.Catal.,2006,27(10)：899-903；及Apcseet UPC 2009 7th Asia Pacific Congress on Sustainable Energy and Environmental Technologies,「One-pot Conversion of Jerusalem Artichoke Tubers into Polyols」。 Polyols are valuable materials for the manufacture of cold weather fluids, cosmetics, polyesters and many other synthetic products. The production of polyols from olefins derived from sugar rather than fossil fuels can be a more environmentally friendly and economically attractive process. Previously, polyols have been produced from polyhydroxy compounds, see WO 2006/092085 and US 2004/0175806. Recently, catalytic conversion of sugars to ethylene glycol on supported carbide catalysts is disclosed in Catalysis Today, 147, (2009) 77-85. US 2010/0256424, US 2010/0255983 and WO 2010/060345 teach a method for preparing ethylene glycol from sugars and a tungsten carbide catalyst for catalyzing the reaction. In Angew. Chem. Int. Ed 2008, 47, 8510-8513 and Support Information and Chem. Commun., 2010, 46, 862-864, it has been published that tungsten carbide catalysts have been successfully used in the batch mode of sugar to ethylene glycol. Catalytic conversion. A small amount of nickel was added to the tungsten carbide catalyst in ChemSusChem 2010, 3, 63-66. Other references that disclose catalysts known in the art for the direct conversion of cellulose to ethylene glycol or propylene glycol include WO 2010/060345; US 7,767,867; Chem. Commun., 2010, 46, 6935-6937; Chin. . Catal., 2006, 27(10): 899-903; and Apcseet UPC 2009 7 th Asia Pacific Congress on Sustainable Energy and Environmental Technologies, "One-pot Conversion of Jerusalem Artichoke Tubers into Polyols".
然而，業內仍需要有效地將醣類直接轉化至多元醇之新觸媒系統，且尤其需要可更適於較大規模生產或持續生產之觸媒系統。本文所述用於自含有醣類之原料生產至少一種多元醇之包含至少一種非受載型組份及至少一種受載型組份的觸媒系統解決此需求。 However, there is still a need in the industry for new catalyst systems that efficiently convert sugars directly to polyols, and in particular, catalyst systems that are more suitable for larger scale production or continuous production. The catalyst system described herein for producing at least one polyol from a saccharide-containing material comprising at least one unsupported component and at least one supported component addresses this need.
本發明之一實施例係用於將至少一種醣類轉化至多元醇之觸媒系統，該觸媒系統包含非受載型組份及受載型組份，該非受載型組份包含選自由鎢化合物、鉬化合物及其任一組合組成之群之化合物，該受載型組份包含於固體觸媒載體上之選自由Pt、Pd、Ru、Rh、Ni、Ir及其組合組成之群之活性金屬組份。該固體觸媒載體係選自由碳、Al2O3、ZrO2、SiO2、MgO、CexZrOy、TiO2、SiC、矽鋁氧化物、沸石、黏土及其組合組成之群。非受載型組份與受載型組份之質量比係在1：100至100：1之範圍內，其中受載型組份包含0.05質量%至30質量%經活化金屬。反應混合物中非受載型觸媒組份之濃度係在反應混合物之0.001質 量%至20質量%之範圍內，且反應混合物中受載型觸媒組份之濃度係在反應混合物之0.001質量%至20質量%之範圍內。觸媒系統之非受載型組份可係選自由鎢酸、鉬酸、偏鎢酸銨、鎢之異聚物、鉬之異聚物、鎢酸之異聚物、鉬酸之異聚物及其組合組成之群。 One embodiment of the present invention is a catalyst system for converting at least one saccharide to a polyol, the catalyst system comprising a non-supported component and a supported component, the unsupported component comprising a compound of the group consisting of a tungsten compound, a molybdenum compound and any combination thereof, the supported component comprising a group selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst carrier. Active metal component. The solid catalyst support is selected from the group consisting of carbon, Al 2 O 3 , ZrO 2 , SiO 2 , MgO, Ce x ZrO y , TiO 2 , SiC, lanthanum aluminum oxide, zeolite, clay, and combinations thereof. The mass ratio of the unsupported component to the supported component is in the range of 1:100 to 100:1, wherein the supported component comprises 0.05% to 30% by mass of the activated metal. The concentration of the unsupported catalyst component in the reaction mixture is in the range of 0.001% by mass to 20% by mass of the reaction mixture, and the concentration of the supported catalyst component in the reaction mixture is 0.001% by mass of the reaction mixture. Up to 20% by mass. The unsupported component of the catalyst system may be selected from the group consisting of tungstic acid, molybdic acid, ammonium metatungstate, tungsten heteropolymer, molybdenum heteropolymer, tungstic acid heteropolymer, and molybdic acid heteropolymer. And a group of its combination.
本發明之一實施例係自包含醣類之原料生產至少一種多元醇之製程，其中該製程包含使氫、水及包含至少一種醣類之原料與觸媒系統接觸以生產包含至少一種多元醇之流出物，該觸媒系統包含非受載型組份及受載型組份，該非受載型組份包含選自由鎢化合物、鉬化合物及其任一組合組成之群之化合物，該受載型組份包含於固體觸媒載體上之選自由Pt、Pd、Ru、Rh、Ni、Ir及其組合組成之群之受載型活性金屬組份；及自該該流出物回收該多元醇。該製程可在分批模式操作中或在連續模式操作中操作。 An embodiment of the invention is a process for producing at least one polyol from a saccharide-containing material, wherein the process comprises contacting hydrogen, water, and a feedstock comprising at least one saccharide with a catalyst system to produce at least one polyol. An effluent, the catalyst system comprising a non-supported component and a supported component, the unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof, the loaded type The component comprises a supported active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst support; and the polyol is recovered from the effluent. The process can be operated in batch mode operation or in continuous mode operation.
本發明之另一實施例係自包含至少一種醣類之原料生產至少一種多元醇之連續製程。該製程涉及以連續方式使氫、水及包含至少一種醣類之原料與觸媒系統接觸以生產包含至少一種多元醇之流出物物流；及自該流出物物流回收該多元醇。氫、水及原料係以連續方式流動。流出物物流係以連續方式流動。該製程係採用包含非受載型組份及受載型組份之觸媒系統的催化製程，該非受載型組份包含選自由鎢化合物、鉬化合物及其任一組合組成之群之化合物，該受載型組份包含於固體觸媒載體上之選自由Pt、Pd、Ru、Rh、Ni、Ir及其組合組成之群之受載型活性金屬 組份。 Another embodiment of the invention is a continuous process for producing at least one polyol from a feedstock comprising at least one saccharide. The process involves contacting hydrogen, water, and a feedstock comprising at least one saccharide with a catalyst system in a continuous manner to produce an effluent stream comprising at least one polyol; and recovering the polyol from the effluent stream. Hydrogen, water and raw materials flow in a continuous manner. The effluent stream flows in a continuous manner. The process employs a catalytic process comprising a catalyst system comprising a non-loaded component and a supported component, the unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof. The supported component comprises a supported active metal selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst carrier. Component.
在一實施例中，接觸發生在至少具有第一輸入物流及第二輸入物流之反應區中，該第一輸入物流至少包含含有至少一種醣類之原料，且該第二輸入物流包含氫。該第一輸入物流可在進入反應區之前加壓，且該第二輸入物流可在進入反應區之前加壓並加熱。該第一輸入物流可在進入反應區之前加壓並加熱至低於醣類之熱分解溫度之溫度，且該第二輸入物流可在進入反應區之前加壓並加熱。該第一輸入物流及該第二輸入物流進一步包含水。 In one embodiment, the contacting occurs in a reaction zone having at least a first input stream comprising at least one saccharide and a second input stream comprising hydrogen. The first input stream can be pressurized prior to entering the reaction zone, and the second input stream can be pressurized and heated prior to entering the reaction zone. The first input stream can be pressurized and heated to a temperature below the thermal decomposition temperature of the saccharide prior to entering the reaction zone, and the second input stream can be pressurized and heated prior to entering the reaction zone. The first input stream and the second input stream further comprise water.
在本發明之另一實施例中，所產生之多元醇至少係乙二醇或丙二醇。亦可產生諸如醇類、有機酸類、醛類、單醣類、二醣類、寡醣類、多醣類、酚系化合物、烴類、甘油、解聚木質素及蛋白質等副產物。在一實施例中，可在接觸之前用觸媒藉由諸如以下等技術處理原料：施膠、乾燥、研磨、熱水處理、蒸汽處理、水解、熱解、熱處理、化學處理、生物處理、催化處理或其組合。 In another embodiment of the invention, the polyol produced is at least ethylene glycol or propylene glycol. By-products such as alcohols, organic acids, aldehydes, monosaccharides, disaccharides, oligosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerin, depolymerized lignin, and proteins can also be produced. In one embodiment, the material may be treated with a catalyst prior to contacting by techniques such as sizing, drying, grinding, hot water treatment, steam treatment, hydrolysis, pyrolysis, heat treatment, chemical treatment, biological treatment, catalysis. Processing or a combination thereof.
可在諸如以下等反應器系統中使原料與觸媒系統之至少受載型組份連續接觸：沸騰觸媒床反應器系統、具有觸媒通道之固定化觸媒反應器系統、預反應器系統(augured reactor system)及漿體反應器系統。操作條件之實例包括在100℃至350℃之範圍內之溫度及大於150 psig之氫壓。在一實施例中，反應器系統中之溫度可在150℃至350℃之範圍內，在另一實施例中，反應器系統中之溫度可在200℃至280℃之範圍內。可在(例如)以下條件下在所操作 反應器系統中使原料與觸媒系統連續接觸：水與包含醣類之原料之重量比在1至100之範圍內、觸媒系統(非受載型組份加受載型組份)與包含醣類之原料之重量比大於0.005、pH小於10及滯留時間大於5分鐘。在另一實施例中，觸媒與包含醣類之原料之重量比係大於0.01。可在足以至少維持一部分水呈液相之條件下在所操作之反應區中使氫、水及原料與觸媒接觸。 The feedstock can be continuously contacted with at least the supported component of the catalyst system in a reactor system such as: a boiling catalytic bed reactor system, an immobilized catalytic reactor system with catalyst channels, a prereactor system (augured reactor system) and slurry reactor system. Examples of operating conditions include temperatures in the range of from 100 ° C to 350 ° C and hydrogen pressures in excess of 150 psig. In one embodiment, the temperature in the reactor system can range from 150 °C to 350 °C, and in another embodiment, the temperature in the reactor system can range from 200 °C to 280 °C. Can be operated under (for example) the following conditions In the reactor system, the raw material is continuously contacted with the catalyst system: the weight ratio of water to the raw material containing the sugar is in the range of 1 to 100, the catalyst system (the unsupported component plus the loaded component) and the inclusion The weight ratio of the raw materials of the saccharide is more than 0.005, the pH is less than 10, and the residence time is more than 5 minutes. In another embodiment, the weight ratio of the catalyst to the feedstock comprising the saccharide is greater than 0.01. The hydrogen, water, and feedstock can be contacted with the catalyst in the reaction zone being operated under conditions sufficient to maintain at least a portion of the water in a liquid phase.
來自反應器系統之流出物物流可進一步包含觸媒系統，該觸媒系統可使用諸如以下等技術與流出物物流分離：直接過濾、沉降隨後過濾、液體旋風器、分級分離、離心、使用絮凝劑、沈澱、液體萃取、吸附、蒸發及其組合。視應用而定，受載型觸媒組份、非受載型觸媒組份或二者可與流出物物流分離。 The effluent stream from the reactor system can further comprise a catalyst system that can be separated from the effluent stream using techniques such as direct filtration, sedimentation followed by filtration, liquid cyclones, fractionation, centrifugation, use of flocculants , precipitation, liquid extraction, adsorption, evaporation, and combinations thereof. Depending on the application, the loaded catalyst component, the unsupported catalyst component, or both may be separated from the effluent stream.
本發明涉及觸媒系統及用於自包含至少一種醣類之原料生產至少一種多元醇之製程。觸媒系統包含非受載型組份及受載型組份，該非受載型組份包含選自由鎢化合物、鉬化合物及其任一組合組成之群之化合物，該受載型組份包含於固體觸媒載體上之選自由Pt、Pd、Ru、Rh、Ni、Ir及其組合組成之群之活性金屬組份。適宜固體觸媒載體之實例包括碳、Al2O3、ZrO2、SiO2、MgO、CexZrOy、TiO2、SiC、矽鋁氧化物、沸石、黏土及其組合。該製程涉及使氫、水及包含至少一種醣類之原料與觸媒系統接觸以生產包含至少一種多元醇之流出物，該觸媒系統包含非受載型 組份及受載型組份，該非受載型組份包含選自由鎢化合物、鉬化合物及其任一組合組成之群之化合物，該受載型組份包含於固體觸媒載體上之選自由Pt、Pd、Ru、Rh、Ni、Ir及其組合組成之群之受載型活性金屬組份；及自流出物回收多元醇。該製程可在分批模式操作中或在連續模式操作中操作。當以連續模式操作時，該製程涉及具有高產率及高選擇性之包含醣類之流動原料物流至乙二醇或丙二醇之連續催化轉化。 The present invention relates to a catalyst system and a process for producing at least one polyol from a feedstock comprising at least one saccharide. The catalyst system comprises an unsupported component and a supported component, the unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound and any combination thereof, the supported component being included in An active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst support. Examples of suitable solid catalyst supports include carbon, Al 2 O 3 , ZrO 2 , SiO 2 , MgO, Ce x ZrO y , TiO 2 , SiC, lanthanum aluminum oxide, zeolite, clay, and combinations thereof. The process involves contacting hydrogen, water, and a feedstock comprising at least one saccharide with a catalyst system to produce an effluent comprising at least one polyol comprising a non-loaded component and a supported component. The supported component comprises a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof, and the supported component is contained on a solid catalyst carrier selected from the group consisting of Pt, Pd, Ru, Rh, Ni, a supported active metal component of Ir and a combination thereof; and a polyol recovered from the effluent. The process can be operated in batch mode operation or in continuous mode operation. When operated in a continuous mode, the process involves continuous catalytic conversion of a stream of saccharide-containing feedstock having a high yield and selectivity to ethylene glycol or propylene glycol.
原料包含至少一種醣類，其可係單醣類、二醣類、寡醣類及多醣類中之任何一類且本質上可係可食用、不可食用、非晶形或結晶的。在一實施例中，原料包含由一或若干藉由醣苷鍵結合之單醣類組成的多醣類。多醣類之實例包括肝醣、纖維素、半纖維素、澱粉、幾丁質及其組合。本文所用術語「醣類」意欲包括所有上述類型之醣類，包括多醣類。 The raw material comprises at least one saccharide which may be any of monosaccharides, disaccharides, oligosaccharides and polysaccharides and which may be edible, inedible, amorphous or crystalline in nature. In one embodiment, the feedstock comprises a polysaccharide consisting of one or several monosaccharides bound by glycosidic linkages. Examples of polysaccharides include glycogen, cellulose, hemicellulose, starch, chitin, and combinations thereof. The term "saccharide" as used herein is intended to include all of the above types of sugars, including polysaccharides.
當該醣類係纖維素、半纖維素或其組合時，可實現其他優勢。半纖維素通常理解為若干種比糖更複雜且不如纖維素複雜之醣類中之任一者。將纖維素及半纖維素以經濟方式轉化為有用產物可係永續製程，其降低化石能源消耗且不與人類食品供應直接競爭。纖維素及半纖維素係具有各種有吸引力的來源(例如來自農業生產之殘留物或來自林業或林產品之廢物)之大規模再生資源。由於人類不能消化纖維素及半纖維素，故使用纖維素及/或半纖維素作為原料並不減少食物供應。此外，纖維素及半纖維素可係低 成本廢物型原料材料，在本文中其轉化成高價值產物，例如諸如乙二醇及丙二醇等多元醇。 Other advantages are realized when the saccharide is cellulose, hemicellulose, or a combination thereof. Hemicellulose is generally understood to be any of a number of sugars that are more complex than sugar and less complex than cellulose. The economical conversion of cellulose and hemicellulose into useful products can be a permanent process that reduces fossil energy consumption and does not compete directly with human food supplies. Cellulose and hemicellulose are large-scale renewable resources of various attractive sources, such as residues from agricultural production or waste from forestry or forest products. Since humans cannot digest cellulose and hemicellulose, the use of cellulose and/or hemicellulose as a raw material does not reduce the food supply. In addition, cellulose and hemicellulose can be low A waste-type feedstock material, which is converted herein to a high value product, such as a polyol such as ethylene glycol and propylene glycol.
該製程之包含醣類之原料可衍生自諸如農業作物、林木生物質、廢物材料、再循環材料等來源。實例包括短輪伐期林木、工業廢材、林木殘留物、農業殘留物、能源作物、工業廢水、都市廢水、紙、紙板、織物、衍生自生物質之紙漿、玉米澱粉、甘蔗、穀類、甜菜、肝醣及包含Cm(H2O)n之分子單元結構之其他分子及其組合。可使用多種材料作為聯合原料。關於生物質，原料可係包括纖維素、木質素及半纖維素之完整生物質，或其中多醣類至少部分解聚或其中木質素、半纖維素或二者已至少部分自完整生物質去除之經處理生物質。 The sugar-containing feedstock of the process can be derived from sources such as agricultural crops, forest biomass, waste materials, recycled materials, and the like. Examples include short-rotation forests, industrial waste, forest residues, agricultural residues, energy crops, industrial wastewater, municipal wastewater, paper, cardboard, fabrics, pulp derived from biomass, corn starch, sugar cane, cereals, sugar beets, Hepatic sugars and other molecules comprising a molecular unit structure of C m (H 2 O) n and combinations thereof. A variety of materials can be used as a joint raw material. With regard to biomass, the feedstock may be a complete biomass comprising cellulose, lignin and hemicellulose, or wherein the polysaccharide is at least partially depolymerized or wherein lignin, hemicellulose or both have been at least partially removed from the intact biomass Treated biomass.
本發明之該製程可在分批模式操作中操作，或可在連續模式操作中操作。在分批模式操作中，將必要反應物與觸媒系統組合並使其反應。一段時間後，自反應器去除反應混合物並將其分離以回收產物。高壓釜反應係分批反應之常見實例。雖然該製程可以分批模式操作，但以連續模式、尤其在較大規模操作中操作存在優勢。以下說明將著重於連續模式操作，但以下說明之焦點不限制本發明之範圍。 The process of the present invention can operate in batch mode operation or can operate in continuous mode operation. In batch mode operation, the necessary reactants are combined with the catalyst system and allowed to react. After a period of time, the reaction mixture was removed from the reactor and separated to recover the product. Autoclave reactions are a common example of batch reactions. Although the process can operate in a batch mode, there are advantages to operating in a continuous mode, especially in larger scale operations. The following description will focus on continuous mode operation, but the following description does not limit the scope of the invention.
不同於分批系統操作，在連續製程中，將原料連續引入至反應區中，同時連續抽出流動物流及包含多元醇之產物。材料必須能夠自低壓來源傳輸至反應區中，且產物必須能夠自反應區傳輸至產物回收區中。視操作模式而定， 殘留固體(若存在)必須能夠自反應區去除。 Unlike batch system operation, in a continuous process, the feedstock is continuously introduced into the reaction zone while continuously withdrawing the flow stream and the product comprising the polyol. The material must be capable of being transported from the low pressure source to the reaction zone and the product must be transportable from the reaction zone to the product recovery zone. Depending on the mode of operation, The residual solids, if any, must be capable of being removed from the reaction zone.
在加壓氫環境中處理包含醣類之原料之挑戰係原料可係不可溶固體。因此，可實施對原料之預處理以促進原料之連續傳輸。適宜預處理操作可包括施膠、乾燥、研磨、熱水處理、蒸汽處理、水解、熱解、熱處理、化學處理、生物處理、催化處理及其組合。施膠、研磨或乾燥可產生可在整個連續製程中使用液流或氣流或機械方式流動或移動之大小之固體粒子。化學處理之實例係多醣類之弱酸水解。催化處理之實例係多醣類之催化水解、多醣類之催化氫化或二者，且生物處理之實例係酶促水解。熱水處理、蒸汽處理、熱處理、化學處理、生物處理或催化處理可產生相比於未處理醣類更易傳輸之較低分子量醣類及解聚木質素。適宜預處理技術參見「Catalytic Hydrogenation of Corn Stalk to Ethylene Glycol and 1,2-Propylene Glycol」Jifeng Pang、Mingyuan Zheng、Aiqin Wang及Tao Zhang Ind.Eng.Chem.Res.DOI：10.1021/ie102505y，出版日期(網絡)：2011年4月20日。亦參見US 2002/0059991。 The challenge material that treats the sugar-containing feedstock in a pressurized hydrogen environment can be an insoluble solid. Therefore, pretreatment of the raw materials can be carried out to promote continuous transport of the raw materials. Suitable pretreatment operations can include sizing, drying, grinding, hot water treatment, steam treatment, hydrolysis, pyrolysis, heat treatment, chemical treatment, biological treatment, catalytic treatment, and combinations thereof. Gluing, grinding or drying produces solid particles of a size that can be flowed or moved using a flow or gas stream or mechanically throughout the continuous process. An example of chemical treatment is weak acid hydrolysis of polysaccharides. Examples of catalytic treatment are catalytic hydrolysis of polysaccharides, catalytic hydrogenation of polysaccharides or both, and examples of biological treatment are enzymatic hydrolysis. Hot water treatment, steam treatment, heat treatment, chemical treatment, biological treatment or catalytic treatment can produce lower molecular weight sugars and depolymerized lignin that are more easily transported than untreated sugars. Suitable pretreatment techniques are described in "Catalytic Hydrogenation of Corn Stalk to Ethylene Glycol and 1,2-Propylene Glycol" Jifeng Pang, Mingyuan Zheng, Aiqin Wang and Tao Zhang Ind. Eng. Chem. Res. DOI: 10.1021/ie 102505y, date of publication ( Network): April 20, 2011. See also US 2002/0059991.
處理包含醣類之原料之另一挑戰係醣類具有熱敏感性。在與觸媒接觸之前暴露於過度加熱可導致醣類之不期望熱反應，例如醣類之炭化。在本發明之一實施例中，以與主要氫物流分開之輸入物流將包含醣類之原料提供至含有觸媒之反應區。在此實施例中，反應區具有至少兩個輸入物流。第一輸入物流至少包含含有醣類之原料，且第二輸入物流至少包含氫。水可存在於第一輸入物流、第二輸入物 流或兩個輸入物流中。一些氫亦可存在於具有包含醣類之原料之第一輸入物流中。藉由將包含醣類之原料及氫分開至兩個獨立輸入物流中，氫物流可加熱至超過反應溫度，而亦不會將包含醣類之原料加熱至反應溫度。至少包含含有醣類之原料之第一輸入物流的溫度可經控制，以不超過不期望熱副反應之溫度。例如，至少包含含有醣類之原料之第一輸入物流的溫度可經控制，以不超過醣類之分解溫度或醣類之炭化溫度。第一輸入物流、第二輸入物流或二者可在引入至反應區中之前加壓至反應壓力。 Another challenge in processing saccharide-containing materials is that the saccharide is thermally sensitive. Exposure to excessive heating prior to contact with the catalyst can result in undesirable thermal reactions of the sugar, such as charring of the sugar. In one embodiment of the invention, the feedstock comprising the saccharide is provided to the reaction zone containing the catalyst in an input stream separate from the main hydrogen stream. In this embodiment, the reaction zone has at least two input streams. The first input stream comprises at least a saccharide-containing feedstock and the second input stream comprises at least hydrogen. Water may be present in the first input stream, the second input Flow or two input streams. Some hydrogen may also be present in the first input stream having a feedstock comprising sugars. By separating the sugar-containing feedstock and hydrogen into two separate input streams, the hydrogen stream can be heated above the reaction temperature without heating the sugar-containing feedstock to the reaction temperature. The temperature of the first input stream comprising at least the saccharide-containing material can be controlled to not exceed the temperature of the undesirable thermal side reaction. For example, the temperature of the first input stream comprising at least the saccharide-containing material can be controlled to not exceed the decomposition temperature of the saccharide or the carbonization temperature of the saccharide. The first input stream, the second input stream, or both may be pressurized to the reaction pressure prior to introduction into the reaction zone.
在連續處理實施例中，在任一預處理後將包含醣類之原料作為流動物流連續引入至催化反應區中。水及氫、兩種反應物均存在於反應區中。如上文所論述且視具體實施例而定，至少一部分氫可分開引入且獨立於包含醣類之原料，或可將反應物之任一組合(包括包含醣類之原料)組合並一起引入至反應區。由於可能存在於反應區中之混合相，具體類型之反應器系統較佳。例如，適宜反應器系統包括沸騰觸媒床反應器系統、具有觸媒通道之固定化觸媒反應器系統、預反應器系統、流體化床反應器系統、機械混合反應器系統及漿體反應器系統(亦稱為三相氣泡塔反應器系統)。 In a continuous treatment embodiment, the feedstock comprising the saccharide is continuously introduced as a flow stream into the catalytic reaction zone after any pretreatment. Water and hydrogen, both reactants, are present in the reaction zone. As discussed above and depending on the particular embodiment, at least a portion of the hydrogen may be introduced separately and independently of the saccharide-containing material, or any combination of reactants (including saccharide-containing materials) may be combined and introduced together into the reaction. Area. A particular type of reactor system is preferred due to the mixed phase that may be present in the reaction zone. For example, suitable reactor systems include boiling catalytic bed reactor systems, immobilized catalytic reactor systems with catalyst channels, pre-reactor systems, fluidized bed reactor systems, mechanically mixed reactor systems, and slurry reactors. System (also known as three-phase bubble column reactor system).
此外，反應器系統之冶金經選擇以在操作條件之範圍內與反應物及期望產物相容。反應器系統之適宜冶金之實例包括鈦、鋯、不銹鋼、具有耐氫脆化塗層之碳鋼、具有耐腐蝕塗層之碳鋼。在一實施例中，反應系統之冶金包括鋯 塗佈或包覆之碳鋼。 In addition, the metallurgy of the reactor system is selected to be compatible with the reactants and desired products within the operating conditions. Examples of suitable metallurgy for reactor systems include titanium, zirconium, stainless steel, carbon steel with a hydrogen embrittlement resistant coating, carbon steel with a corrosion resistant coating. In one embodiment, the metallurgy of the reaction system comprises zirconium Coated or coated carbon steel.
在反應區內且在操作條件下，反應物經歷催化轉化反應以產生至少一種多元醇。期望多元醇包括乙二醇及丙二醇。亦可生產副產物且其包括諸如醇類、有機酸類、醛類、單醣類、醣類、酚系化合物、烴類、甘油、解聚木質素、碳水化合物及蛋白質等化合物。除產物多元醇以外，副產物可具有價值並可回收。反應可繼續進行至完成，或一些反應物及中間物可與產物一起以混合物形式保留。本文中作為副產物之一部分所包括之中間物可包括諸如解聚纖維素、木質素及半纖維素等化合物。未反應氫、水及醣類亦可連同產物及副產物一起存在於反應區流出物中。未反應材料及/或中間物可經回收並再循環至反應區。 The reactants undergo a catalytic conversion reaction to produce at least one polyol in the reaction zone and under operating conditions. Polyols are expected to include ethylene glycol and propylene glycol. By-products can also be produced and include compounds such as alcohols, organic acids, aldehydes, monosaccharides, sugars, phenolic compounds, hydrocarbons, glycerol, depolymerized lignin, carbohydrates, and proteins. In addition to the product polyol, by-products can be of value and can be recycled. The reaction can be continued until completion, or some of the reactants and intermediates can be retained as a mixture with the product. The intermediates included as part of the by-products herein may include compounds such as depolymerized cellulose, lignin, and hemicellulose. Unreacted hydrogen, water, and sugars may also be present in the reaction zone effluent along with the product and by-products. Unreacted materials and/or intermediates can be recovered and recycled to the reaction zone.
反應係催化反應且反應區包含至少一種觸媒系統。將醣類轉化至至少一種多元醇之觸媒系統包含非受載型組份，該非受載型組份包含選自由鎢化合物、鉬化合物及其任一組合組成之群之化合物；及受載型組份，該受載型組份包含於固體觸媒載體上之選自由Pt、Pd、Ru、Rh、Ni、Ir及其組合組成之群之活性金屬組份。多種活性金屬可存在於固體觸媒載體上。適宜非受載型組份之實例包括鎢酸、鉬酸、鎢酸銨、偏鎢酸銨、仲鎢酸銨、包含至少一種第I族或第II族元素之鎢酸鹽化合物、包含至少一種第I族或第II族元素之偏鎢酸鹽化合物、包含至少一種第I族或第II族元素之仲鎢酸鹽化合物、鎢之異聚物、鉬之異聚物、氧化鎢、氧化鉬及其組合。一或多種非受載型觸媒組份可與一 或多種受載型觸媒組份一起使用。觸媒系統亦可視為多組份觸媒，且該等術語在本文中可互換使用。 The reaction system catalyzes the reaction and the reaction zone contains at least one catalyst system. A catalyst system for converting a saccharide to at least one polyol comprises a non-supported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof; and a loaded type A component, the supported component comprising an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof, on a solid catalyst support. A plurality of active metals can be present on the solid catalyst support. Examples of suitable non-supported components include tungstic acid, molybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one Group I or Group II element, including at least one Group I Or a metatungstate compound of a Group II element, a paratungstate compound comprising at least one Group I or Group II element, a heteropolymer of tungsten, a heteropolymer of molybdenum, tungsten oxide, molybdenum oxide, and combinations thereof . One or more non-loaded catalyst components can be combined with one Or use together with a variety of loaded catalyst components. Catalytic systems can also be considered as multi-component catalysts, and such terms are used interchangeably herein.
觸媒系統之受載型觸媒組份需要固體觸媒載體。載體可呈粉末形狀或諸如以下等具體形狀：球體、擠出物、丸劑、顆粒、錠劑、不規則形狀粒子、單片結構、催化塗佈管或催化塗佈之熱交換器表面。活性金屬可以業內已知的適宜方式(例如藉由與載體一起共沈澱、共擠出，或浸漬)納於催化載體上。活性金屬可呈還原形式。可使用耐火氧化物觸媒載體及其他載體。耐火無機氧化物載體之實例包括(但不限於)二氧化矽、氧化鋁、二氧化矽-氧化鋁、氧化鈦、氧化鋯、氧化鎂、黏土、沸石、分子篩等。應指出，二氧化矽-氧化鋁並非二氧化矽與氧化鋁之混合物，而係意指已共凝膠或共沈澱之酸性非晶形材料。亦可採用碳及經活化碳作為載體。具體適宜載體包括碳、經活化碳、Al2O3、ZrO2、SiO2、MgO、CexZrOy、TiO2、SiC、矽鋁氧化物、沸石、黏土及其組合。當然，可使用材料之組合作為載體。活性金屬可構成受載型觸媒組份之0.05質量%至30質量%。在本發明之另一實施例中，活性金屬可構成受載型觸媒組份之0.3質量%至15質量%，且在本發明之另一實施例中，活性金屬可構成受載型觸媒組份之0.5質量%至7質量%。 The supported catalyst component of the catalyst system requires a solid catalyst carrier. The carrier may be in the form of a powder or a specific shape such as a sphere, extrudate, pellet, granule, lozenge, irregularly shaped particle, monolithic structure, catalytic coating tube or catalytically coated heat exchanger surface. The active metal can be supported on the catalytic support in a suitable manner known in the art (e.g., by coprecipitation, coextrusion, or impregnation with the support). The active metal can be in reduced form. A refractory oxide catalyst carrier and other supports can be used. Examples of refractory inorganic oxide supports include, but are not limited to, ceria, alumina, ceria-alumina, titania, zirconia, magnesia, clay, zeolites, molecular sieves, and the like. It should be noted that cerium oxide-alumina is not a mixture of cerium oxide and aluminum oxide, but means an acidic amorphous material which has been co-gelled or co-precipitated. Carbon and activated carbon can also be used as a carrier. Specific suitable supports include carbon, activated carbon, Al2O3, ZrO2, SiO2, MgO, CexZrOy, TiO2, SiC, yttrium aluminum oxide, zeolite, clay, and combinations thereof. Of course, a combination of materials can be used as the carrier. The active metal may constitute 0.05% by mass to 30% by mass of the supported catalyst component. In another embodiment of the present invention, the active metal may constitute 0.3% by mass to 15% by mass of the supported catalyst component, and in another embodiment of the present invention, the active metal may constitute a loaded catalyst. The component is from 0.5% by mass to 7% by mass.
該製程中所用觸媒系統之量可在包含醣類之原料之0.005質量%至0.4質量%範圍內。在其他實施例中，該製程中所用觸媒系統之量可在包含醣類之原料之0.01質量%至 0.25質量%範圍內。在又一些實施例中，該製程中所用觸媒系統之量可在包含醣類之原料之0.02質量%至0.15質量%範圍內。所發生之反應係多步驟反應，且可使用不同量之觸媒系統或觸媒系統中不同相對量之組份來控制不同反應之速率。關於觸媒系統之量或所用觸媒系統中組份之相對量，個別應用可有不同要求。反應混合物中非受載型觸媒組份之濃度係在0.001質量%至20質量%之範圍內，且反應混合物中受載型觸媒組份之濃度係在0.001質量%至20質量%之範圍內。在觸媒系統內，非受載型組份與受載型組份之質量比係在1：100至100：1之範圍內，如藉由ICP或其他常見的濕式化學方法所量測。在另一實施例中，非受載型組份與受載型組份之質量比係在1：20至50：1之範圍內，且非受載型組份與受載型組份之質量比係在1：10至10：1之範圍內。 The amount of the catalyst system used in the process may range from 0.005 mass% to 0.4 mass% of the raw material containing the sugar. In other embodiments, the amount of the catalyst system used in the process may be from 0.01% by mass of the raw material containing the sugar to Within the range of 0.25 mass%. In still other embodiments, the amount of catalyst system used in the process can range from 0.02% to 0.15% by mass of the saccharide-containing material. The reaction that occurs is a multi-step reaction, and different amounts of the catalyst system or components of different relative amounts in the catalyst system can be used to control the rate of the different reactions. Individual applications may have different requirements regarding the amount of catalyst system or the relative amount of components in the catalyst system used. The concentration of the unsupported catalyst component in the reaction mixture is in the range of 0.001% by mass to 20% by mass, and the concentration of the supported catalyst component in the reaction mixture is in the range of 0.001% by mass to 20% by mass. Inside. In the catalyst system, the mass ratio of the unsupported component to the supported component is in the range of 1:100 to 100:1, as measured by ICP or other common wet chemical methods. In another embodiment, the mass ratio of the unsupported component to the loaded component is in the range of 1:20 to 50:1, and the mass of the unsupported component and the loaded component is The ratio is in the range of 1:10 to 10:1.
在本發明之一實施例中，非受載型觸媒組份可係在反應條件下可溶於反應混合物或至少部分可溶於反應混合物之固體，該反應混合物至少包括水及原料。有效量之非受載型觸媒應可溶於反應混合物。不同應用及不同非受載型觸媒組份將導致反應混合物溶液中所需之非受載型觸媒組份之有效量不同。在本發明之另一實施例中，非受載型觸媒組份係可與反應混合物混溶或至少部分混溶之液體。如固體非受載型觸媒組份一樣，有效量之液體非受載型觸媒應混溶於反應混合物中。再次，不同應用及不同非受載型觸媒組份將導致需混溶於反應混合物中之非受載型觸媒組份 之有效量不同。通常，混溶於水中之非受載型觸媒組份之量係在1%至100%、在另一實施例中10%至100%、且在又一實施例中20%至100%之範圍內。 In one embodiment of the invention, the unsupported catalyst component can be soluble in the reaction mixture or at least partially soluble in the reaction mixture under reaction conditions, the reaction mixture comprising at least water and a feedstock. An effective amount of the non-loaded catalyst should be soluble in the reaction mixture. Different applications and different unsupported catalyst components will result in different effective amounts of the unsupported catalyst components required in the reaction mixture solution. In another embodiment of the invention, the non-accepted catalyst component is a liquid that is miscible or at least partially miscible with the reaction mixture. An effective amount of liquid non-loaded catalyst should be miscible in the reaction mixture, as is the solid non-loaded catalyst component. Again, different applications and different unsupported catalyst components will result in non-loaded catalyst components that need to be miscible in the reaction mixture. The effective amount is different. Typically, the amount of the unsupported catalyst component that is miscible in water is between 1% and 100%, in another embodiment from 10% to 100%, and in yet another embodiment from 20% to 100%. Within the scope.
本發明之多組份觸媒可提供若干個優於更傳統的單一組份觸媒之優勢。例如，可降低觸媒之製造成本，此乃因較少活性組份需要納於固體觸媒載體上。可降低操作成本，此乃因預期將需要較少觸媒補充且可使用更具選擇性處理步驟用於觸媒回收及再循環。其他優勢包括：經改良觸媒穩定性，此使得觸媒消耗較低及每單位之多元醇產物成本較低；及改良對乙二醇及丙二醇之選擇性且降低諸如丁二醇等共沸雜質之產量的潛力。 The multi-component catalyst of the present invention provides several advantages over the more traditional single component catalysts. For example, the manufacturing cost of the catalyst can be reduced because less active components are required to be supported on the solid catalyst support. Operating costs can be reduced as less catalyst supplementation is expected and more selective processing steps can be used for catalyst recovery and recycling. Other advantages include improved catalyst stability, which results in lower catalyst consumption and lower cost per unit of polyol product; and improved selectivity to ethylene glycol and propylene glycol and reduced azeotropic impurities such as butanediol The potential for production.
在一些實施例中，觸媒系統可含於反應區內，且在其他實施例中，觸媒可連續或間歇地穿過反應區，且在又一些實施例中，觸媒系統可存在兩種情況，其中至少一種觸媒系統組份存在於反應區中，而其他觸媒系統組份連續或間隙地穿過反應區。適宜反應器系統包括沸騰觸媒床反應器系統、具有觸媒通道之固定化觸媒反應器系統、預反應器系統、流體化床反應器系統、機械混合反應器系統及漿體反應器系統(亦稱為三相氣泡塔反應器系統)及其組合。 In some embodiments, the catalyst system can be contained within the reaction zone, and in other embodiments, the catalyst can pass through the reaction zone continuously or intermittently, and in still other embodiments, the catalyst system can exist in two In the case where at least one of the catalyst system components is present in the reaction zone while the other catalyst system components pass through the reaction zone continuously or intermittently. Suitable reactor systems include a boiling catalytic bed reactor system, an immobilized catalytic reactor system with catalyst channels, a pre-reactor system, a fluidized bed reactor system, a mechanical mixing reactor system, and a slurry reactor system ( Also known as a three-phase bubble column reactor system) and combinations thereof.
反應器系統中之操作條件之實例包括在100℃至350℃之範圍內之溫度及大於150 psig之氫壓。在一實施例中，反應器系統中之溫度可在150℃至350℃之範圍內，在另一實施例中，反應器系統中之溫度可在200℃至280℃之範圍 內。可在以下條件下在反應器系統中使包含至少一種醣類之原料與觸媒系統連續接觸：水與原料重量比在1至100之範圍內、觸媒(非受載型組份+受載型組份)與原料重量比大於0.005、pH小於10及滯留時間大於5分鐘。在另一實施例中，水與原料重量比係在1至20之範圍內且觸媒與原料重量比大於0.01。在再一實施例中，水與原料重量比係在1至5之範圍內且觸媒與原料重量比大於0.1。 Examples of operating conditions in the reactor system include temperatures in the range of from 100 ° C to 350 ° C and hydrogen pressures in the range of greater than 150 psig. In one embodiment, the temperature in the reactor system can range from 150 ° C to 350 ° C. In another embodiment, the temperature in the reactor system can range from 200 ° C to 280 ° C. Inside. The feedstock comprising at least one saccharide can be continuously contacted with the catalyst system in a reactor system under the following conditions: water to feedstock weight ratio in the range of 1 to 100, catalyst (non-loaded component + loaded) The weight ratio of the component to the raw material is greater than 0.005, the pH is less than 10, and the residence time is greater than 5 minutes. In another embodiment, the weight ratio of water to feedstock is in the range of from 1 to 20 and the catalyst to feedstock weight ratio is greater than 0.01. In still another embodiment, the weight ratio of water to feedstock is in the range of from 1 to 5 and the catalyst to feedstock weight ratio is greater than 0.1.
在本發明之一實施例中，催化反應系統採用漿體反應器。漿體反應器係亦稱為三相氣泡塔反應器。漿體反應器系統為本技術所熟知，且漿體反應器系統之實例係闡述於US 5,616,304及專題報告Slurry Reactor Design Studies,DOE計劃第DE-AC22-89PC89867號Reactor Cost Comparisons中，其可參見http：//www.fischer-tropsch.org/DOE/DOE_reports/91005752/de91005752_toc.htm。觸媒系統可與水及包含醣類之原料混合以形成漿體，將該漿體引導至漿體反應器。反應發生在漿體反應器內，且觸媒與流出物物流一起傳輸離開反應器系統。漿體反應器系統可在上文所列條件下操作。在另一實施例中，催化反應系統採用沸騰床反應器。沸騰床反應器系統為本技術所熟知，且沸騰床反應器系統之實例係闡述於US 6,436,279中。 In one embodiment of the invention, the catalytic reaction system employs a slurry reactor. Slurry reactors are also known as three-phase bubble column reactors. Slurry reactor systems are well known in the art, and examples of slurry reactor systems are described in US 5,616,304 and in the special report Slurry Reactor Design Studies, DOE Plan DE-AC22-89 PC89867 Reactor Cost Comparisons, see http ://www.fischer-tropsch.org/DOE/DOE_reports/91005752/de91005752_toc.htm. The catalyst system can be mixed with water and a feedstock comprising sugar to form a slurry that is directed to the slurry reactor. The reaction takes place in the slurry reactor and the catalyst is transported away from the reactor system along with the effluent stream. The slurry reactor system can be operated under the conditions listed above. In another embodiment, the catalytic reaction system employs an ebullated bed reactor. Ebullated bed reactor systems are well known in the art, and examples of bubbling bed reactor systems are set forth in US 6,436,279.
來自反應區之流出物物流至少含有產物多元醇，且亦可含有未反應水、氫、醣類、諸如酚系化合物及甘油等副產物及諸如解聚多醣類及木質素等中間物。視所選觸媒及所用催化反應系統而定，流出物物流亦可至少含有一部分觸 媒系統。流出物物流可含有一部分呈液相之觸媒系統，或一部分呈固相之觸媒系統。在一些實施例中，在回收期望產物或副產物之前或之後自流出物物流去除固相觸媒組份可係有利的。可使用一或多個諸如以下等技術自流出物物流去除固相觸媒組份：直接過濾、沉降隨後過濾、液體旋風器、分級分離、離心、使用絮凝劑、沈澱、萃取、蒸發或其組合。在一實施例中，可將分離之觸媒再循環至反應區。 The effluent stream from the reaction zone contains at least the product polyol, and may also contain unreacted water, hydrogen, sugars, by-products such as phenolic compounds and glycerin, and intermediates such as depolymerized polysaccharides and lignin. Depending on the catalyst selected and the catalytic reaction system used, the effluent stream may also contain at least a portion of the contact Media system. The effluent stream may contain a portion of the catalyst system in the liquid phase, or a portion of the catalyst system in a solid phase. In some embodiments, it may be advantageous to remove the solid phase catalyst component from the effluent stream before or after recovery of the desired product or by-product. The solid phase catalyst component can be removed from the effluent stream using one or more techniques such as direct filtration, sedimentation followed by filtration, liquid cyclones, fractionation, centrifugation, use of flocculants, precipitation, extraction, evaporation, or combinations thereof. . In one embodiment, the separated catalyst can be recycled to the reaction zone.
參見圖1，經由物流122將觸媒系統、水及包含醣類之原料引導至反應區124。物流122中之混合物具有(例如)5之水與包含醣類之原料之重量比及0.05之觸媒系統與包含醣類之原料之重量比。經由物流125將至少氫引導至反應區124。反應區124係在(例如)250℃之溫度、1200 psig之氫壓、7之pH及8分鐘之滯留時間下操作。在引入至反應區124中之前，使物流122中之觸媒、水及包含醣類之原料及物流125中之氫達到1800 psig之壓力，以處於與反應區124相同之壓力下。然而，僅將至少包含氫之物流125升高至至少250℃，以處於大於或等於反應區124中之溫度之溫度下。對物流122中至少含有醣類之混合物進行溫度控制，以保持在低於醣類之分解或炭化溫度之溫度下。在反應區124中，將醣類催化轉化成至少乙二醇或丙二醇。反應區流出物126至少含有產物乙二醇或丙二醇。反應區流出物126亦可含有醇類、有機酸類、醛類、單醣類、多醣類、酚系化合物、烴類、甘油、解聚木質素及蛋白質。將反應 區流出物126引導至產物回收區134，在產物回收區134中將期望之二醇產物分離並於蒸汽136中回收。自產物回收區134於物流138中去除反應區流出物126之其餘組份。 Referring to Figure 1, the catalyst system, water, and feedstock containing sugar are directed to reaction zone 124 via stream 122. The mixture in stream 122 has, for example, a weight ratio of water of 5 to the raw material comprising the saccharide and a weight ratio of the catalyst system of 0.05 to the raw material comprising the saccharide. At least hydrogen is directed to reaction zone 124 via stream 125. Reaction zone 124 is operated at, for example, a temperature of 250 ° C, a hydrogen pressure of 1200 psig, a pH of 7 and a residence time of 8 minutes. The catalyst, water, and sugar-containing feedstock in stream 122 and the hydrogen in stream 125 are brought to a pressure of 1800 psig prior to introduction into reaction zone 124 to be at the same pressure as reaction zone 124. However, only the stream 125 comprising at least hydrogen is raised to at least 250 ° C to be at a temperature greater than or equal to the temperature in the reaction zone 124. The mixture containing at least the saccharide in stream 122 is temperature controlled to maintain a temperature below the decomposition or carbonization temperature of the saccharide. In reaction zone 124, the saccharide is catalytically converted to at least ethylene glycol or propylene glycol. The reaction zone effluent 126 contains at least the product ethylene glycol or propylene glycol. The reaction zone effluent 126 may also contain alcohols, organic acids, aldehydes, monosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerol, depolymerized lignin, and proteins. Will react Zone effluent 126 is directed to product recovery zone 134 where the desired glycol product is separated and recovered in steam 136. The remaining components of the reaction zone effluent 126 are removed from the product recovery zone 134 in stream 138.
參見圖2，將水及包含多醣類之原料210引入至預處理單元220，在預處理單元220中將醣類研磨至小至足以與水一起作為漿體使用習用設備泵送之粒子大小。將預處理原料與管線219中之水及管線223中之觸媒系統組合，且將合併物流227引導至反應區224。合併物流227具有(例如)20之水與包含醣類之原料之重量比及0.1之觸媒系統與醣類重量比。經由物流225將至少氫引導至反應區224。可在反應區224之前將一些氫與物流227組合，如藉由可選虛線221所顯示。反應區224係在(例如)280℃之溫度、200 psig之氫壓、7之pH及8分鐘之滯留時間下操作。在引入至反應區224中之前，使物流227中之觸媒系統、水及包含醣類之預處理原料及物流225中之氫達到1800 psig之壓力，以處於與反應區224相同之壓力下。然而，僅將至少包含氫之物流225升高至至少250℃，以處於大於或等於反應區224之溫度之溫度下。對物流227中至少含有醣類之混合物進行溫度控制，以保持在低於多醣類之分解或炭化溫度之溫度下。在反應區224中，將醣類催化轉化成至少乙二醇或或聚乙二醇。 Referring to Figure 2, water and a feedstock 210 comprising a polysaccharide are introduced to a pretreatment unit 220 where the sugar is ground to a particle size small enough to be pumped with water as a slurry using conventional equipment. The pretreated feedstock is combined with the water in line 219 and the catalyst system in line 223 and the combined stream 227 is directed to reaction zone 224. The combined stream 227 has, for example, a weight ratio of water of 20 to the raw material comprising the sugar and a catalyst system to sugar weight ratio of 0.1. At least hydrogen is directed to reaction zone 224 via stream 225. Some of the hydrogen may be combined with stream 227 prior to reaction zone 224, as indicated by the optional dashed line 221. Reaction zone 224 is operated at, for example, a temperature of 280 ° C, a hydrogen pressure of 200 psig, a pH of 7 and a residence time of 8 minutes. The catalyst system in stream 227, the water and the pretreatment feedstock containing the sugar and the hydrogen in stream 225 are brought to a pressure of 1800 psig prior to introduction into reaction zone 224 to be at the same pressure as reaction zone 224. However, only stream 225 comprising at least hydrogen is raised to at least 250 °C to be at a temperature greater than or equal to the temperature of reaction zone 224. The mixture containing at least the saccharide in stream 227 is temperature controlled to maintain a temperature below the decomposition or charring temperature of the polysaccharide. In reaction zone 224, the saccharide is catalytically converted to at least ethylene glycol or polyethylene glycol.
反應區流出物226至少含有產物乙二醇或丙二醇及觸媒。反應區流出物226亦可含有醇類、有機酸類、醛類、單醣類、多醣類、酚系化合物、烴類、甘油、解聚木質素 及蛋白質。將反應區流出物226引導至可選觸媒系統回收區228，在回收區228中將觸媒組份與反應區流出物226分離並在管線232中去除。可視情況使管線232中之觸媒組份再循環以與管線223合併或再循環至反應區224，如藉由可選虛線229所顯示。將觸媒組份空乏之反應區流出物230引導至產物回收區234，在產物回收區234中將期望之二醇產物分離並於蒸汽236中回收。自產物回收區234於物流238中去除流出物230之其餘組份。 The reaction zone effluent 226 contains at least the product ethylene glycol or propylene glycol and a catalyst. Reaction zone effluent 226 may also contain alcohols, organic acids, aldehydes, monosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerin, depolymerized lignin And protein. The reaction zone effluent 226 is directed to an optional catalyst system recovery zone 228 where the catalyst component is separated from the reaction zone effluent 226 and removed in line 232. The catalyst component in line 232 may optionally be recycled to be combined with or recycled to reaction zone 224, as indicated by optional dashed line 229. The reaction zone effluent 230, which is depleted in the catalyst component, is directed to a product recovery zone 234 where the desired glycol product is separated and recovered in steam 236. The remaining components of the effluent 230 are removed from the product recovery zone 234 in stream 238.
根據以下程序實施十七個實驗。將1克含有原料之醣類及100克去離子水添加至300 ml Parr高壓釜反應器中。將有效量之含有受載型及非受載型組份之觸媒添加至反應器中。原料之細節及觸媒之類型及量係顯示於表1中。將高壓釜密封並用N2隨後用H2吹洗，並最後在室溫下利用H2加壓至6 MPa。在1000 rpm之持續攪拌下將高壓釜加熱至245℃並保持在溫度下30分鐘。30分鐘後，將高壓釜冷卻至室溫，且藉由過濾來回收液體產物並使用HPLC進行分析。自Sigma-Aldrich獲得微晶纖維素。使用初濕技術藉由使用存於水中之硝酸Ni將不同量之Ni浸漬於經活化碳載體Norit-CA1上來製備於Norit CA-1上之Ni觸媒。然後在40℃下於烘箱中在氮吹洗下將經浸漬載體乾燥過夜，並在750℃下於H2中還原1 hr。5% Pd/C及% Pt/C係購自Johnson Matthey。以所產生乙二醇或丙二醇之質量除以所用原料之質量並乘以100來量測乙二醇及丙二醇產率。 Seventeen experiments were performed according to the following procedure. One gram of sugar containing the starting material and 100 grams of deionized water were added to a 300 ml Parr autoclave reactor. An effective amount of the catalyst containing the supported and unsupported components is added to the reactor. The details of the raw materials and the type and amount of the catalyst are shown in Table 1. The autoclave was sealed with N 2 and then purged with H 2, and finally the use of H 2 at room temperature was pressurized to 6 MPa. The autoclave was heated to 245 ° C with continuous stirring at 1000 rpm and kept at temperature for 30 minutes. After 30 minutes, the autoclave was cooled to room temperature, and the liquid product was recovered by filtration and analyzed using HPLC. Microcrystalline cellulose was obtained from Sigma-Aldrich. The Ni catalyst on Norit CA-1 was prepared by incipient wetness technique by immersing different amounts of Ni on the activated carbon support Norit-CA1 using Ni nitrate in water. The impregnated support was then dried overnight in an oven under nitrogen purge at 40 ° C and reduced in H 2 at 750 ° C for 1 hr. 5% Pd/C and % Pt/C were purchased from Johnson Matthey. The ethylene glycol and propylene glycol yields were determined by dividing the mass of ethylene glycol or propylene glycol produced by the mass of the starting materials used and multiplying by 100.
122‧‧‧物流 122‧‧‧ Logistics
124‧‧‧反應區 124‧‧‧Reaction zone
125‧‧‧物流 125‧‧‧ Logistics
126‧‧‧反應區流出物 126‧‧‧Reaction zone effluent
134‧‧‧產物回收區 134‧‧‧Product recovery area
136‧‧‧蒸汽 136‧‧‧Steam
138‧‧‧物流 138‧‧‧ Logistics
210‧‧‧水及包含多醣類之原料 210‧‧‧Water and raw materials containing polysaccharides
219‧‧‧管線 219‧‧‧ pipeline
220‧‧‧預處理單元 220‧‧‧Pretreatment unit
223‧‧‧管線 223‧‧‧ pipeline
224‧‧‧反應區 224‧‧‧Reaction zone
225‧‧‧物流 225‧‧‧ Logistics
226‧‧‧反應區流出物 226‧‧‧Reaction zone effluent
227‧‧‧合併物流 227‧‧‧Combined logistics
228‧‧‧可選觸媒系統回收區 228‧‧‧Optional Catalyst System Recovery Zone
230‧‧‧反應區流出物 230‧‧‧Reaction zone effluent
232‧‧‧管線 232‧‧‧ pipeline
234‧‧‧產物回收區 234‧‧‧Product recovery area
236‧‧‧蒸汽 236‧‧‧Steam
238‧‧‧物流 238‧‧‧ Logistics
圖1係本發明之一實施例之流程方案之基本圖式。未繪示理解本發明所不需要之設備及處理步驟。 1 is a basic diagram of a flow scheme of an embodiment of the present invention. Equipment and processing steps not required to understand the present invention are not shown.
圖2係本發明之另一實施例之流程方案之基本圖式，其顯示可選預處理區及具有可選受載型觸媒組份再循環之可選受載型觸媒組份分離區。未繪示理解本發明所不需要之設備及處理步驟。 2 is a basic diagram of a flow scheme of another embodiment of the present invention showing an optional pretreatment zone and an optional load-bearing catalyst component separation zone having an optional loaded catalyst component recycle . Equipment and processing steps not required to understand the present invention are not shown.
122‧‧‧物流 122‧‧‧ Logistics
124‧‧‧反應區 124‧‧‧Reaction zone
125‧‧‧物流 125‧‧‧ Logistics
126‧‧‧反應區流出物 126‧‧‧Reaction zone effluent
134‧‧‧產物回收區 134‧‧‧Product recovery area
136‧‧‧蒸汽 136‧‧‧Steam
138‧‧‧物流 138‧‧‧ Logistics
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| US13/192,907 US20110312487A1 (en) | 2011-07-28 | 2011-07-28 | Catalyst system for generation of polyols from saccharides |
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| US4642394A (en) * | 1985-07-16 | 1987-02-10 | Celanese Corporation | Production of propanediols |
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| CN102049273B (en) * | 2009-10-27 | 2013-05-01 | 中国科学院大连化学物理研究所 | Mesoporous carbon-supported tungsten carbide catalyst and preparation and application thereof |
| CN101768050B (en) * | 2009-12-25 | 2012-12-05 | 北京大学 | Method for preparing ethylene glycol and 1,2-propylene glycol |
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| CN102190562B (en) * | 2010-03-17 | 2014-03-05 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol from polyols |
| US8222465B2 (en) * | 2011-07-28 | 2012-07-17 | Uop Llc | Catalytic process for continuously generating polyols |
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- 2012-07-03 WO PCT/US2012/045343 patent/WO2013015955A2/en active Application Filing
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| EP2736869A2 (en) | 2014-06-04 |
| WO2013015955A2 (en) | 2013-01-31 |
| CN103608320A (en) | 2014-02-26 |
| EP2736869A4 (en) | 2015-01-07 |
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