TW201307267A

TW201307267A - Process for recovering alcohol

Info

Publication number: TW201307267A
Application number: TW101126178A
Authority: TW
Inventors: Adam Orosco; Manuel Salado; Lincoln Sarager; R Jay Warner; Trinity Horton; Victor J Johnston; David Lee
Original assignee: Celanese Int Corp
Priority date: 2011-08-03
Filing date: 2012-07-20
Publication date: 2013-02-16

Abstract

Recovery of an alcohol such as ethanol from a crude alcohol product, preferably obtained from the hydrogenation of acetic acid using a low energy process. The crude ethanol product is separated in a column to produce a distillate stream comprising ethyl acetate and a residue stream comprising ethanol, acetic acid, and water. The ethanol product is recovered in a second column as an ethanol side stream.

Description

回收乙醇之製程 Process for recovering ethanol

本發明一般涉及到生產乙醇的製程，尤其是從包含乙醇、醋酸乙酯、醋酸和水的乙醇粗產物回收乙醇之製程。 The present invention relates generally to a process for producing ethanol, and more particularly to a process for recovering ethanol from a crude ethanol product comprising ethanol, ethyl acetate, acetic acid and water.

工業使用的乙醇傳統生產方式是來自石化原料、例如石油、天然氣和煤炭而生產得之，或者是從進料中間體，例如合成氣而生產得之，或者是自澱粉質原料或纖維素原料，例如玉米或甘蔗，而生產得之。傳統上利用來自石化原料以及纖維素原料來生產乙醇的方法包含乙烯之酸催化水合、甲醇類同系化反應、直接醇類合成法以及”費托合成法”((Fischer-Tropsch synthesis))。不穩定性石化原料價格會引起傳統方式生產乙醇的成本波動，當原料價格上漲時，會使得以替代來源來生產乙醇的需求更為增加。澱粉原料以及纖維素原料可發酵轉化為乙醇。然而發酵方法通常用於消費性乙醇生產，由此產生的乙醇也可以適用於供燃料之用或人類食用。此外，澱粉或纖維素原料的發酵會和作為食物來源相競爭，因而限制乙醇可用於工業生產的量。 The traditional production method of ethanol used in industry is produced from petrochemical raw materials such as petroleum, natural gas and coal, or from feed intermediates such as syngas, or from starchy raw materials or cellulose raw materials. For example, corn or sugar cane is produced. Conventional methods for producing ethanol from petrochemical feedstocks and cellulosic feedstocks include ethylene acid catalyzed hydration, methanol homologation, direct alcohol synthesis, and "Fischer-Tropsch synthesis". The price of unstable petrochemical feedstocks can cause fluctuations in the cost of ethanol produced in the traditional way. When the price of raw materials rises, the demand for alternative sources to produce ethanol will increase. The starch raw material and the cellulose raw material can be fermentatively converted into ethanol. However, fermentation methods are commonly used for consumer ethanol production, and the ethanol produced therefrom can also be used for fuel or human consumption. In addition, the fermentation of starch or cellulosic feedstock will compete with the source of food, thus limiting the amount of ethanol that can be used in industrial production.

藉由烷酸類和/或其他羰基化合物的還原以生產乙醇已被廣泛研究，而已在文獻中提到各種觸媒及支撐體(supports)的組合和操作條件。在還原例如醋酸之烷酸( )類時，其他化合物會和乙醇一起形成或藉由副反應形成。這些雜質會限制從這樣的反應混合物來生產和回收乙醇。例如在氫化製程中，酯、乙醇和/或水會一起產出，而形成共沸物，而這是很難分離的。此外，當轉化是不完全的，未反應的醋酸仍然會殘存在於反應器產物之中，而其必須予以移除以回收乙醇。 The production of ethanol by reduction of alkanoic acids and/or other carbonyl compounds has been extensively studied, and combinations and operating conditions of various catalysts and supports have been mentioned in the literature. In the reduction of alkanoic acids such as acetic acid, other compounds may be formed together with ethanol or by side reactions. These impurities can limit the production and recovery of ethanol from such reaction mixtures. For example, in a hydrogenation process, esters, ethanol, and/or water are produced together to form an azeotrope, which is difficult to separate. Furthermore, when the conversion is incomplete, unreacted acetic acid will still remain in the reactor product, which must be removed to recover the ethanol.

歐洲專利EP02060553描述碳氫化合物轉成乙醇的製程，包括將碳氫化合物轉成為醋酸，然後使醋酸氫化而得乙醇。分離來自氫化反應器的物流，以獲取乙醇流及醋酸和醋酸乙酯的物流，而該物流再循環到氫化反應器。 European Patent EP02060553 describes a process for the conversion of hydrocarbons to ethanol, which involves the conversion of hydrocarbons to acetic acid followed by hydrogenation of acetic acid to give ethanol. The stream from the hydrogenation reactor is separated to obtain a stream of ethanol and a stream of acetic acid and ethyl acetate, and the stream is recycled to the hydrogenation reactor.

目前仍需要改善從還原例如醋酸之烷酸類，和/或其他含羰基化合物所獲得之粗產物中回收乙醇的製程。 There is still a need to improve the process for recovering ethanol from the reduction of crude products such as acetic acid alkanoic acids, and/or other carbonyl containing compounds.

本發明涉及從乙醇粗產物回收例如乙醇的醇類之低能量製程。在一實施方式中，本發明提供一種用於生產乙醇的製程，包括在反應器中觸媒的存在下氫化醋酸，而形成乙醇粗產物。在第一蒸餾塔分離至少一部分的乙醇粗產物，而產生包含醋酸乙酯的餾出物，和包含乙醇、醋酸和水的第一殘留物。使送入第一蒸餾塔乙醇粗產物中大部分的乙醇在第一殘留物移出。在第二蒸餾塔中分離至少一部分的第一殘留物，而產生包含乙醇的側流，和包含殘餘醋酸和/或水的第二殘留物。較佳者為，第二蒸餾塔也形成第二餾出物，以便從第一殘留物分離殘餘的醋酸乙酯。 This invention relates to a low energy process for recovering alcohols such as ethanol from crude ethanol products. In one embodiment, the present invention provides a process for producing ethanol comprising hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product. At least a portion of the crude ethanol product is separated in the first distillation column to produce a distillate comprising ethyl acetate, and a first residue comprising ethanol, acetic acid and water. Most of the ethanol fed to the crude ethanol product of the first distillation column is removed from the first residue. At least a portion of the first residue is separated in the second distillation column to produce a side stream comprising ethanol, and a second residue comprising residual acetic acid and/or water. Preferably, the second distillation column also forms a second distillate to separate residual ethyl acetate from the first residue.

因此，在一實施方式中，本發明提供生產乙醇的製程，其包括如下的步驟：(a)在反應器中觸媒的存在下，氫化醋酸形成乙醇粗產物；(b)在第一蒸餾塔中分離至少一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇的第一殘留物；及(c)在第二蒸餾塔中從至少一部分的第一殘留物回收乙醇側流。 Accordingly, in one embodiment, the present invention provides a process for producing ethanol comprising the steps of: (a) hydrogenating acetic acid to form a crude ethanol product in the presence of a catalyst in a reactor; (b) in a first distillation column Separating at least a portion of the crude ethanol product to produce a first distillate comprising ethyl acetate, and a first residue comprising ethanol; and (c) recovering from at least a portion of the first residue in the second distillation column Lateral flow of ethanol.

第二蒸餾塔也較佳者為形成第二餾出物，其中包含至少有1重量%的醋酸乙酯或至少5重量%的醋酸乙酯，且製程可進一步包括將至少一部分的第二餾出物再循環回到反應器的步驟。乙醇側流較佳者為包含至少50重量%的乙醇，或至少88重量%的乙醇。至少一部分的第一餾出物可視情況選擇性地返回到反應器。 The second distillation column is also preferably formed to form a second distillate comprising at least 1% by weight of ethyl acetate or at least 5% by weight of ethyl acetate, and the process may further comprise at least a portion of the second distillate The step of recycling the reactants back to the reactor. Preferably, the ethanol side stream comprises at least 50% by weight ethanol, or at least 88% by weight ethanol. At least a portion of the first distillate may optionally be returned to the reactor as appropriate.

在另一實施方式中，本發明提供生產乙醇的製程，其包括如下的步驟：(a)提供包含乙醇和醋酸乙酯之乙醇粗產物，(b)在第一蒸餾塔中分離至少一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇的第一殘留物；及(c)從第二蒸餾塔中至少一部分的第一殘留物回收乙醇側流。 In another embodiment, the invention provides a process for producing ethanol comprising the steps of: (a) providing a crude ethanol product comprising ethanol and ethyl acetate, and (b) separating at least a portion of the ethanol in the first distillation column The crude product produces a first distillate comprising ethyl acetate, and a first residue comprising ethanol; and (c) recovering an ethanol side stream from at least a portion of the first residue in the second distillation column.

在另一實施方式中，本發明提供生產乙醇的製程，包括在反應器中觸媒的存在下氫化醋酸，而形成乙醇粗產物；在第一蒸餾塔分離一部分的乙醇粗產物，而得包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸及水的第一殘留物，其中被送入第一蒸餾塔的乙醇粗產物中大部分乙醇在第一殘留物移除；在第二蒸餾塔分離至少一部分的第一殘留物，而產生包含乙醇的側流，和包含水及殘餘醋酸的第二殘留物。較佳者為將至少有70%在乙醇粗產物的乙醇移除於第一殘留物流中。第一殘留物可視情況選擇性地於70至155℃的溫度由第一蒸餾塔排出。 In another embodiment, the present invention provides a process for producing ethanol, comprising hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product; separating a portion of the crude ethanol product in the first distillation column to obtain acetic acid. a first distillate of ethyl ester, and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol fed to the first distillation column is removed from the first residue; in the second distillation The column separates at least a portion of the first residue to produce a side stream comprising ethanol, and a second residue comprising water and residual acetic acid. Preferably, at least 70% of the ethanol in the crude ethanol product is removed from the first residue stream. The first residue may optionally be discharged from the first distillation column at a temperature of 70 to 155 °C.

在另一實施方式中，發明提供生產乙醇的製程中，包括：(a)提供乙醇粗產物；(b)在第一蒸餾塔分離一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸及水的第一殘留物，其中將在乙醇粗產物的大部分乙醇移除於第一殘留物中；以及(c)在第二蒸餾塔分離至少一部分的第一殘留物，而產生包含乙醇的側流，和包含水及殘餘醋酸的第二殘留物。 In another embodiment, the invention provides a process for producing ethanol comprising: (a) providing a crude ethanol product; (b) separating a portion of the crude ethanol product in the first distillation column to produce a first distillation product comprising ethyl acetate And a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the crude ethanol product is removed from the first residue; and (c) separating at least a portion of the first distillation column The residue produces a side stream comprising ethanol and a second residue comprising water and residual acetic acid.

在另一實施方式中，本發明提供生產乙醇的製程，包括：(a)在反應器中觸媒的存在下氫化醋酸，而形成乙醇粗產物；(b)在第一蒸餾塔中分離一部分的乙醇粗產物，而得包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸及水的第一殘留物，其中在送到蒸餾塔的乙醇粗產物中大部分的乙醇被移除於第一殘留物中；及 (c)在第二蒸餾塔分離至少一部分的第一殘留物，而產生包含殘留醋酸乙酯的第二餾出物，和包含乙醇的側流。 In another embodiment, the invention provides a process for producing ethanol comprising: (a) hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product; (b) separating a portion of the first distillation column a crude ethanol product to obtain a first distillate comprising ethyl acetate, and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the crude ethanol product sent to the distillation column is removed a residue; and (c) separating at least a portion of the first residue in the second distillation column to produce a second distillate comprising residual ethyl acetate, and a side stream comprising ethanol.

在另一實施方式中，本發明提供生產乙醇的製程，包括提供包含乙醇、醋酸乙酯、水、及醋酸之乙醇粗產物；在第一蒸餾塔分離一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸及水的第一殘留物，其中饋入蒸餾塔的大部分乙醇移除於第一殘留物中；並在第二蒸餾塔中分離至少一部分的第一殘留物，而產生包含殘留醋酸乙酯的第二餾出物，和包含乙醇的側流。 In another embodiment, the present invention provides a process for producing ethanol, comprising providing a crude ethanol product comprising ethanol, ethyl acetate, water, and acetic acid; separating a portion of the crude ethanol product in the first distillation column to produce a product comprising acetic acid a first distillate of the ester, and a first residue comprising ethanol, acetic acid, and water, wherein a majority of the ethanol fed to the distillation column is removed from the first residue; and at least a portion of the second distillation column is separated The first residue produces a second distillate comprising residual ethyl acetate and a side stream comprising ethanol.

在一方面，製程還包括在水解裝置水解至少一部分的第一餾出物，而形成包含乙醇和醋酸的水解產物之步驟，並可視情況選擇性地將至少一部分的水解產物導入反應器。用於可視情況選擇性的水解步驟之水，例如可得自至少一部分的第二殘留物。 In one aspect, the process further includes the step of hydrolyzing at least a portion of the first distillate in the hydrolysis unit to form a hydrolysate comprising ethanol and acetic acid, and optionally introducing at least a portion of the hydrolyzate to the reactor. Water for the optionally hydrolyzing step can be obtained, for example, from at least a portion of the second residue.

較佳者為，至少有70%乙醇粗產物中的乙醇移除於第一殘留物流中。所獲得之第一殘留物可包含從10至75重量%的乙醇，從0.01至35重量%的醋酸，及25至70重量%的水。第一餾出物可視情況選擇性地包含從10到85重量%的醋酸乙酯、從0.1到70%的乙醛、低於55重量%的乙醇，以及低於20重量%的水。 Preferably, at least 70% of the ethanol in the crude ethanol product is removed from the first residue stream. The first residue obtained may comprise from 10 to 75% by weight of ethanol, from 0.01 to 35% by weight of acetic acid, and from 25 to 70% by weight of water. The first distillate may optionally comprise from 10 to 85% by weight ethyl acetate, from 0.1 to 70% acetaldehyde, less than 55% by weight ethanol, and less than 20% by weight water.

製程中可視情況選擇性地還包括，減少側流含水量而產生水含量降低的乙醇產物流。因此，在一方面，製程還包括用分離膜來分離至少一部分的側流，而形成包含水的滲透流，與包含乙醇和水的截留流(retentate stream)，而該截留流之水含量低於至少一部分側流的水含量。在另一實施方式中，製程可視情況選擇性地還包括以一種或多種萃取劑來萃取至少一部分的側流，而產生具水含量降低的乙醇產物流。由此產生的側流可包含75至96重量%的乙醇，低於12重量%的水，低於1重量%的醋酸，和低於5重量%的醋酸乙酯。較佳者為，側流包含低於1重量%的醋酸乙酯和低於3重量%的水。 Optionally, the process optionally includes reducing the water content of the side stream to produce a stream of ethanol product having a reduced water content. Thus, in one aspect, the process further includes separating the at least a portion of the side stream with a separation membrane to form a permeate stream comprising water, and a retentate stream comprising ethanol and water, the water content of the retentate stream being less than The water content of at least a portion of the side stream. In another embodiment, the process optionally includes extracting at least a portion of the side stream with one or more extractants to produce a stream of ethanol product having a reduced water content. The side stream thus produced may comprise from 75 to 96% by weight of ethanol, less than 12% by weight of water, less than 1% by weight of acetic acid, and less than 5% by weight of ethyl acetate. Preferably, the side stream comprises less than 1% by weight ethyl acetate and less than 3% by weight water.

在一方面，醋酸從甲醇和一氧化碳形成，用於氫化步驟的每一甲醇、一氧化碳和氫氣均衍生自合成氣，而該合成氣係衍生自碳源，該碳源其係選自由天然氣、原油、石油、煤炭、生物料及其組合所組成之群組。 In one aspect, acetic acid is formed from methanol and carbon monoxide, and each of the methanol, carbon monoxide, and hydrogen used in the hydrogenation step is derived from a synthesis gas derived from a carbon source selected from the group consisting of natural gas, crude oil, A group of oil, coal, biomass, and combinations thereof.

序論 Preface

詳而言之，本發明涉及到在觸媒存在下氫化醋酸產物中回收乙醇的製程。氫化反應產生乙醇粗產物，其包含乙醇、水、醋酸乙酯、醋酸、和其他雜質。本發明的製程涉及在第一蒸餾塔分離乙醇粗產物，而產生包含乙醇、水、及醋酸的第一殘留物流，和包含醋酸乙酯的第一餾出物流。在第二蒸餾塔分離至少一部分的第一殘留物流，而產生包括殘留醋酸乙酯的第一餾出物，乙醇側流和包含水及殘餘醋酸的第二殘留物。乙醇側流可構成一種適於銷售之適合多種應用的乙醇組成物，或者可進一步處理，例如除去殘留的水。有利的是，這種分離方法可用減少能源需求之方式來從乙醇粗產物回收乙醇。 In particular, the present invention relates to a process for recovering ethanol from a hydrogenated acetic acid product in the presence of a catalyst. The hydrogenation reaction produces a crude ethanol product comprising ethanol, water, ethyl acetate, acetic acid, and other impurities. The process of the present invention involves separating the crude ethanol product in a first distillation column to produce a first residue stream comprising ethanol, water, and acetic acid, and a first distillate stream comprising ethyl acetate. At least a portion of the first residue stream is separated in the second distillation column to produce a first distillate comprising residual ethyl acetate, an ethanol side stream, and a second residue comprising water and residual acetic acid. The ethanol side stream can constitute an ethanol composition suitable for a variety of applications suitable for sale, or can be further processed, for example, to remove residual water. Advantageously, this separation process recovers ethanol from the crude ethanol product in a manner that reduces energy requirements.

在回收乙醇時，本發明製程使用各種塔，較佳者為使用蒸餾塔。在較佳的實施方式中，第一殘留物流包含來自乙醇粗產物中很大一部分的乙醇、水、和醋酸。第一殘留物流，例如可包含來自乙醇粗產物中至少50%的乙醇，較佳者為至少有70%的乙醇。就範圍而言，殘留物流可包含來自乙醇粗產物中從50%到97.5%的乙醇，尤佳者為從70%至99.9%的乙醇。在第一殘留物中回收乙醇粗產物的乙醇量可高於97.5%，例如，高於99.9%，而乙醇粗產物的醋酸乙酯濃度低於2重量%。在一些實施方式中，根據醋酸乙酯濃度，若在第一殘留物取出太多乙醇，則在第一殘留物會導致不良的醋酸乙酯洩漏，雖然下面將討論第二蒸餾塔能夠移除洩漏到第一殘留物中殘餘的醋酸乙酯。較佳者為只有少量醋酸乙酯，如果有的話，在第一殘留物中抽移。在一些實施方式中，第一殘留物包含低於1,000重量ppm，低於100重量ppm，低於50重量ppm的醋酸乙酯。在其他方面，第一殘留物可包含較大量的醋酸乙酯，因為第二蒸餾塔有能力移除殘留的醋酸乙酯。例如，第一殘留物可包含高達0.1重量%的醋酸乙酯，高達0.5重量%的醋酸乙酯，或高達1重量%的醋酸乙酯。 In the recovery of ethanol, the process of the present invention uses various columns, preferably a distillation column. In a preferred embodiment, the first residual stream comprises a significant portion of the ethanol from the crude ethanol, water, and acetic acid. The first residual stream, for example, may comprise at least 50% ethanol from the crude ethanol product, preferably at least 70% ethanol. In terms of ranges, the residual stream may comprise from 50% to 97.5% ethanol in the crude ethanol product, and more preferably from 70% to 99.9% ethanol. The amount of ethanol recovered from the crude ethanol product in the first residue may be higher than 97.5%, for example, higher than 99.9%, and the ethyl acetate concentration of the crude ethanol product is less than 2% by weight. In some embodiments, depending on the ethyl acetate concentration, if too much ethanol is withdrawn from the first residue, the first residue will cause a poor ethyl acetate leak, although the second distillation column will be able to remove the leak as discussed below. Residual ethyl acetate to the first residue. Preferably, only a small amount of ethyl acetate, if any, is removed in the first residue. In some embodiments, the first residue comprises less than 1,000 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight of ethyl acetate. In other aspects, the first residue may comprise a larger amount of ethyl acetate because The two distillation column has the ability to remove residual ethyl acetate. For example, the first residue may comprise up to 0.1% by weight of ethyl acetate, up to 0.5% by weight of ethyl acetate, or up to 1% by weight of ethyl acetate.

在較佳的實施方式中，第一殘留物包含來自乙醇粗產物主要部分的水和醋酸。第一殘留物可包含來自乙醇粗產物中，例如，至少有80%的水，尤佳者為至少90%的水。就範圍而言，第一殘留物較佳者為包含來自乙醇粗產物中從80%至99.4%的水，較佳者為從90%到99.4%的水。殘留物流可包含來自乙醇粗產物中至少有85%的醋酸，例如至少有90%，而尤佳者為約100%的醋酸。就範圍而言，殘留物流較佳者為包含來自乙醇粗產物中從85%至100%的醋酸，尤佳者為從90%到100%的醋酸。在一實施方式中，實質上所有的醋酸回收於殘留物流中。 In a preferred embodiment, the first residue comprises water and acetic acid from a major portion of the crude ethanol product. The first residue may comprise from the crude ethanol product, for example, at least 80% water, and more preferably at least 90% water. In terms of ranges, the first residue preferably comprises from 80% to 99.4% water, preferably from 90% to 99.4% water from the crude ethanol product. The residual stream may comprise at least 85% acetic acid from the crude ethanol product, such as at least 90%, and more preferably about 100% acetic acid. In terms of ranges, the residual stream preferably comprises from 85% to 100% acetic acid in the crude ethanol product, and more preferably from 90% to 100% acetic acid. In one embodiment, substantially all of the acetic acid is recovered in the residual stream.

可進一步分離包含乙醇、水和醋酸的第一殘留物，以回收乙醇。在一較佳的實施方式中，在第二蒸餾塔可移除水和醋酸於第二殘留物中。 The first residue comprising ethanol, water and acetic acid can be further separated to recover ethanol. In a preferred embodiment, water and acetic acid are removed from the second residue in the second distillation column.

在典型的實施方式中，根據本發明製程中初始蒸餾塔的能源需求可低於5.5百萬英熱單位(MMBtu)/每噸成品乙醇，例如，每噸成品乙醇低於4.5百萬英熱單位，或每噸成品乙醇低於3.5百萬英熱單位。 In a typical embodiment, the energy demand of the initial distillation column in the process according to the invention may be less than 5.5 million British thermal units (MMBtu) per ton of finished ethanol, for example, less than 4.5 million British thermal units per ton of finished ethanol. , or less than 3.5 million British thermal units per ton of finished ethanol.

來自第一蒸餾塔之餾出物可包含輕有機物，例如醋酸乙酯和乙醛。從第一蒸餾塔的乙醇粗產物中移除這些成分組成物提供一種有效移除輕有機物的手段。此外，若使用多座蒸餾塔，則因乙醇不會來攜帶輕有機物，從而減少從輕有機物所形成的副產物。在一實施方式中，輕有機物返回到反應器中，而該反應器可轉化乙醛和醋酸乙酯成為額外的乙醇。因此，全部或部分的第一餾出物可再循環到氫化反應器。在一些實施方式中，輕有機物可予以分離，使得一支主要包含乙醛和/或醋酸乙酯的物流返回到反應器。在另一實施方式中，輕有機物可從系統中加以吹氣清除(purged)。 The distillate from the first distillation column may comprise light organics such as ethyl acetate and acetaldehyde. Removal of these constituents from the crude ethanol product of the first distillation column provides a means of effectively removing light organics. In addition, if a plurality of distillation columns are used, since the ethanol does not carry light organic matter, the by-product formed from the light organic matter is reduced. In one embodiment, the light organics are returned to the reactor, which converts acetaldehyde and ethyl acetate to additional ethanol. Thus, all or part of the first distillate can be recycled to the hydrogenation reactor. In some embodiments, the light organics can be separated such that a stream comprising primarily acetaldehyde and/or ethyl acetate is returned to the reactor. In another embodiment, the light organic matter can be purged from the system.

醋酸之氫化Hydrogenation of acetic acid

本發明的製程可用於任何生產乙醇的氫化製程。下面進一步說明可用於醋酸氫化的物料、觸媒、反應條件和分離製程。 The process of the present invention can be used in any hydrogenation process for producing ethanol. The materials, catalysts, reaction conditions, and separation processes that can be used for the hydrogenation of acetic acid are further described below.

用於本發明製程的原料-醋酸、和氫氣，可衍生自自任何合適的來源，包括天然氣、石油、煤炭、生物料等。舉例而言，通過甲醇羰基化、乙醛氧化、乙烯氧化、氧化發酵、厭氣發酵等，可生產醋酸。適合於生產醋酸之甲醇羰基化製程介紹於美國專利號7,208,624、7,115,772、7,005,541、6,657,078、6,627,770、6,143,930、5,599,976、5,144,068、5,026,908、5,001,259和4,994,608，其全部揭露在此納入參考。或者可視情況選擇地，可將乙醇生產和這些甲醇羰基化製程整合在一起。 The feedstocks used in the process of the present invention - acetic acid, and hydrogen, may be derived from any suitable source, including natural gas, petroleum, coal, biomass, and the like. For example, acetic acid can be produced by methanol carbonylation, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation, anaerobic fermentation, and the like. Methanol carbonylation processes suitable for the production of acetic acid are described in U.S. Patent Nos. 7,208,624, 7,115,772, 7,005, 541, 6, 657, 078, 6, 627, 770, 6, 143, 930, 5, 599, 976, 5, 144, 068, 5, 026, 908, 5, 001, 259, and 4, 994, 608, the entire disclosures of each of which are incorporated herein by reference. Alternatively, ethanol production can be integrated with these methanol carbonylation processes.

由於石油和天然氣價格波動而忽起忽落，利用備用碳源來生產醋酸，以及像是甲醇和一氧化碳之中間體的方法，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，由其它便利可得的碳源所衍生的合成氣("syn gas")來生產醋酸可能會成為有利的。例如美國專利第6,232,352號所揭露改裝甲醇廠以生產醋酸的方法，在此可納入做為參考。通過改裝甲醇廠，可顯著地減少或大部分移除新建醋酸廠大量的資本成本，以及其所伴隨產生的一氧化碳。由甲醇合成循環((methanol synthesis loop))衍生產出全部或部分合成氣，其並被提供至分離裝置以回收一氧化碳，將其然後再用以來生產醋酸。藉以類似的方式，用於氫化步驟的氫氣也可由合成氣來提供。 The use of alternative carbon sources to produce acetic acid, as well as methods such as intermediates of methanol and carbon monoxide, has generated increasing interest as oil and natural gas prices fluctuate. In particular, when the price of oil is higher than that of natural gas, it may be advantageous to produce acetic acid from a syngas derived from other readily available carbon sources ("syn gas"). A method of modifying a methanol plant to produce acetic acid is disclosed, for example, in U.S. Patent No. 6,232,352, which is incorporated herein by reference. By modifying the methanol plant, significant capital costs, as well as the carbon monoxide that is associated with it, can be significantly reduced or largely removed. Derived from a methanol synthesis loop produces all or part of the synthesis gas, which is supplied to a separation unit to recover carbon monoxide, which is then used to produce acetic acid. In a similar manner, the hydrogen used in the hydrogenation step can also be provided by syngas.

在一些實施方式中，上面所描述的醋酸氫化製程中部分或所有的原料可部分或全部衍生自合成氣。例如，醋酸可由甲醇和一氧化碳所形成，它們都可來自合成氣。可以藉由部分的氧化重整((oxidation reforming))或蒸汽重整((steam reforming))來形成合成氣，而一氧化碳可從合成氣分離得之。同樣地，用於氫化醋酸以形成乙醇粗產物的氫氣可由合成氣分離得之。合成氣又可轉而來自不同的碳源。碳源，例如，可以選自由天然氣、原油、石油、煤炭、生物料及其組合所組成之群組。合成氣或氫氣，也可得自生物源衍生之甲烷氣體，如垃圾填埋場或農業廢棄物生物產生之生物源衍生的甲烷氣體。 In some embodiments, some or all of the feedstock in the acetic acid hydrogenation process described above may be derived in part or in whole from the syngas. For example, acetic acid can be formed from methanol and carbon monoxide, all of which can be derived from syngas. The synthesis gas can be formed by partial oxidation reforming or steam reforming, and carbon monoxide can be separated from the synthesis gas. Similarly, hydrogen used to hydrogenate acetic acid to form a crude ethanol product can be separated from the synthesis gas. Syngas can in turn be derived from different carbon sources. The carbon source, for example, may be selected from the group consisting of natural gas, crude oil, petroleum, coal, biomass, and combinations thereof. Group of. Syngas or hydrogen can also be obtained from biologically derived methane gas, such as methane gas derived from biological sources produced by landfills or agricultural waste.

在另一實施方式中，用於氫化步驟之醋酸可從生物料發酵形成。發酵製程中較佳者為採用醋化((acetogenic))製程或藉由同質醋化((homoacetogenic))微生物來使糖發酵而產生醋酸，以及產生如果存有的話，也會是很少的作為副產物之二氧化碳。發酵製程的碳效率較佳者為高於70%，高於80%或高於90%，而傳統的酵母製程其通常碳效率約為67%。可視情況選擇地，用於發酵製程的微生物為一菌屬(genus)選自由梭狀芽孢桿菌、乳酸桿菌、摩雷拉梭狀芽孢桿菌、嗜熱性嫌氣性細菌、丙酸菌、丙酸梭狀芽孢桿菌、革蘭氏陰性厭氧菌和絲桿菌所組成之群組，且尤其是菌種(species)係選自由蘋果酸梭菌、酪酸梭菌、摩雷拉嗜熱性梭菌、奇韋嗜熱性嫌氣性細菌、德布魯基乳酸菌、丙酸細菌、丙酸螺旋菌、蘇辛尼克厭氧菌、乳酸菌類桿菌和內切葡聚醣酶桿菌所組成之群組。在這個製程中可視情況選擇性地全部或部分來自生物料未發酵的殘留物，例如：木酚素((lignans))，可氣化形成氫氣，其可用於本發明之氫化步驟。形成醋酸之典型發酵製程揭露於美國專利號6,509,180、6,927,048、7,074,603、7,507,562、7,351,559、7,601,865、7,682,812和7,888,082，其全部內容在此納入參考。另見美國專利申請公開案號2008/0193989和2009/0281354，其全部內容在此納入參考。 In another embodiment, the acetic acid used in the hydrogenation step can be formed from fermentation of the biomass. Preferably, the fermentation process uses an acetogenic process or a homoacetogenic microorganism to ferment the sugar to produce acetic acid, and if present, there are few Carbon dioxide as a by-product. The carbon efficiency of the fermentation process is preferably greater than 70%, greater than 80% or greater than 90%, whereas conventional yeast processes typically have a carbon efficiency of about 67%. Optionally, the microorganism used in the fermentation process is a genus selected from the group consisting of Clostridium, Lactobacillus, Clostridium Morrow, Thermophilic anaerobic bacteria, Propionic acid bacteria, Propionate prop. a group consisting of Bacillus, Gram-negative anaerobic bacteria and Mycobacterium, and especially the species selected from Clostridium malic acid, Clostridium butyricum, Clostridium thermophilus, and Chivi A group consisting of a thermophilic anaerobic bacterium, a De Brucella lactic acid bacterium, a propionic acid bacterium, a propionic acid Helicobacter, a Susinnik anaerobic bacterium, a lactic acid bacterium, and an endoglucanase bacterium. Optionally, in this process, all or part of the unfermented residue from the biomass, such as lignans, may be vaporized to form hydrogen which may be used in the hydrogenation step of the present invention. Typical fermentation processes for the formation of acetic acid are disclosed in U.S. Patent Nos. 6,509,180, 6,927,048, 7,074, 603, 7,507, 562, 7, 351, 559, 7, 601, 865, 7, 682, 812, and 7, 888, 082, the entire disclosure of which is incorporated herein by reference. See also U.S. Patent Application Publication Nos. 2008/0193989 and 2009/0281354, the entire contents of each of which are incorporated herein by reference.

例如，生物料可包含但不限於，農業廢棄物、森林產物、草及其他纖維素材料、木材採伐殘留物、軟木片、硬木片、樹枝、樹樁、樹葉、樹皮、鋸木屑、不合格紙漿、玉米、玉米秸稈、小麥秸稈、稻草、甘蔗殘留物、柳枝稷、芒草、動物糞便、城市垃圾、城市生活污水、商業廢物、葡萄殘留物、杏仁殼、核桃殼、椰子殼、咖啡殘留物、草顆粒、草球、木球、紙板、紙張、塑料和布料。參閱，例如，美國專利第7,884,253號，其全部內容在此納入參考。另一生物料源是黑液 ((black liquor))，一種濃稠深色的液體，是轉化木材成為紙漿((然後將其乾燥製成紙張))之卡夫製程((Kraft process))的副產物。黑液為木質素殘留物、半纖維素和無機化學品的水溶液。 For example, biological materials may include, but are not limited to, agricultural waste, forest products, grass and other cellulosic materials, wood harvest residues, cork sheets, hardwood chips, branches, stumps, leaves, bark, sawdust, unqualified pulp, Corn, corn stover, wheat straw, straw, sugarcane residues, switchgrass, miscanthus, animal manure, municipal waste, municipal sewage, commercial waste, grape residue, almond shell, walnut shell, coconut shell, coffee residue, grass granule , grass balls, wood balls, cardboard, paper, plastic and cloth. See, for example, U.S. Patent No. 7,884,253, the disclosure of which is incorporated herein by reference. Another source of biological material is black liquor ((black liquor), a thick, dark liquid, a by-product of the Kraft process that converts wood into pulp (and then drys it into paper). Black liquor is an aqueous solution of lignin residues, hemicellulose, and inorganic chemicals.

美國再發證專利RE35,377號，在此也納入參考，其提供藉由炭素材料，例如像是石油、煤炭、天然氣和生物料轉化來生產甲醇之方法。這個製程包含固體和/或液體炭素材料之氫化氣化((hydrogasification))以獲取製程氣體，其藉由額外天然氣進行蒸汽熱解而形成合成氣。合成氣轉化為甲醇，該甲醇再經羰基化則可得醋酸。該方法也同樣地可產生氫氣，其如上所述可用於本發明。美國專利第5,821,111號，其中揭示廢棄生物料通過氣化轉化成合成氣的製程，和美國專利第6,685,754號揭示含氫氣體態組成物，例如包含氫氣和一氧化碳之合成氣之製法，其全部內容在此納入參考。 U.S. Reissue Patent No. RE35,377, incorporated herein by reference, which is incorporated herein by reference in its entirety in its entirety in the the the the the the the the the the This process involves hydrohydrogenation of solid and/or liquid carbon materials to obtain a process gas that is steam pyrolyzed by additional natural gas to form a syngas. The synthesis gas is converted to methanol, which is then carbonylated to give acetic acid. The process also produces hydrogen gas as such, which can be used in the present invention as described above. U.S. Patent No. 5,821,111, the disclosure of which is incorporated herein by reference in its entirety, the disclosure of the disclosure of the disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of Inclusion in the reference.

饋入氫化反應的醋酸也可包含其他羧酸類及其酸酐類，以及乙醛和丙酮。較佳者為合適的醋酸進料流包含一種或更多種化合物係選自由醋酸、醋酐、乙醛、醋酸乙酯及其混合物所組成之群組。這些其他化合物也可在本發明的製程中被氫化。在一些實施方式中，羧酸類，例如丙酸或其酐，的存在，可以是有益於生產丙醇。水也可存在於醋酸進料中。 The acetic acid fed to the hydrogenation reaction may also contain other carboxylic acids and their anhydrides, as well as acetaldehyde and acetone. Preferably, the suitable acetic acid feed stream comprises one or more compounds selected from the group consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof. These other compounds can also be hydrogenated in the process of the invention. In some embodiments, the presence of a carboxylic acid, such as propionic acid or its anhydride, can be beneficial for the production of propanol. Water can also be present in the acetic acid feed.

另外，可直接採用來自美國專利第6,657,078號所介紹描述的甲醇羰基化裝置的閃蒸槽之蒸汽形式的醋酸來作為粗產物，該美國專利全部內容在此納入參考。例如，該粗蒸汽產物可直接饋入本發明乙醇合成反應區而不需要冷凝醋酸和輕餾份或移除水，進而可節約總處理成本。 In addition, acetic acid in the form of a vapor from a flash tank of a methanol carbonylation unit as described in U.S. Patent No. 6,657,078, which is incorporated herein by reference in its entirety, is incorporated herein by reference. For example, the crude steam product can be fed directly into the ethanol synthesis reaction zone of the present invention without the need to condense acetic acid and light ends or remove water, thereby saving overall processing costs.

醋酸可在反應溫度蒸發，隨後蒸發的醋酸可用以未稀釋狀態之氫或以例如氮氣、氬氣、氦氣、二氧化碳之類的相對惰性載氣所稀釋之氫一起饋入反應器。為使反應在氣相中操作，應控制系統中溫度使得溫度不低於醋酸之露點。在一實施方式中，醋酸可在特定壓力下的醋酸沸點蒸發，然後蒸發的醋酸可進一步被加熱至反應器入口溫度。在另一實施方式中，該醋酸於蒸發前與其他氣體混合，然後加熱該混合蒸汽到反應器入口溫度。較佳者為，在溫度等於或低於125℃，使氫氣和/或回收氣體通過醋酸，而將醋酸轉移至蒸汽狀態，接著將該合併後氣體流加熱到反應器入口溫度。 The acetic acid can be evaporated at the reaction temperature, and the evaporated acetic acid can be fed to the reactor together with hydrogen in an undiluted state or hydrogen diluted with a relatively inert carrier gas such as nitrogen, argon, helium or carbon dioxide. In order for the reaction to operate in the gas phase, the temperature in the system should be controlled so that the temperature is not below the dew point of acetic acid. In one embodiment, acetic acid can evaporate at the boiling point of acetic acid at a particular pressure, and then the evaporated acetic acid can be further heated to the reactor inlet temperature. In another embodiment, the acetic acid is mixed with other gases prior to evaporation and then the mixed vapor is heated to the reactor. Inlet temperature. Preferably, the hydrogen and/or recovered gas is passed through the acetic acid at a temperature equal to or lower than 125 ° C, and the acetic acid is transferred to a vapor state, and then the combined gas stream is heated to the reactor inlet temperature.

一些醋酸氫化形成乙醇製程的實施方式中可使用多種配置，包含固定床反應器或流化床反應器。在本發明許多的實施方式中，可以使用”絕熱”反應器；亦即在此些實施方式中，幾乎沒有或根本沒有必要在反應區通入內部管道作熱量之添加或移除。在其他實施方式中，可以使用徑向流動反應器((radial flow reactor))或反應器組，或者可以使用一系列反應器，無論其具或不具熱交換、淬火或引進更多的進料。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之內或一系列其中介入熱交換器之容器((組))。 A number of configurations can be used in some embodiments of the hydrogenation of acetic acid to form an ethanol process, including fixed bed reactors or fluidized bed reactors. In many embodiments of the invention, an "adiabatic" reactor can be used; that is, in such embodiments, there is little or no need to pass an internal conduit into the reaction zone for heat addition or removal. In other embodiments, a radial flow reactor or a reactor set can be used, or a series of reactors can be used, with or without heat exchange, quenching, or introducing more feed. In addition, a shell-and-tube reactor having a heat transfer medium can be used. In many cases, the reaction zone can be placed within a vessel or a series of vessels (groups) in which the heat exchanger is interposed.

在較佳的實施方式中，觸媒用於固定床反應器中，反應器，例如其呈管道或管形狀，其中反應物通常以蒸汽的形式來傳送或通過觸媒。可以採用其他反應器，例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，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。 In a preferred embodiment, the catalyst is used in a fixed bed reactor, such as in the form of a pipe or tube, wherein the reactants are typically delivered in the form of steam or through a catalyst. Other reactors may be employed, such as fluidized or bunk bed reactors. In some cases, the hydrogenation catalyst can be combined with an inert material to adjust the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactants with the catalyst particles.

氫化反應可以在液相或氣相中進行。較佳者為反應在下列情況下以氣相進行。反應溫度可介於125℃至350℃，例如：從200℃至325℃，從225℃至300℃，或從250℃至300℃。壓力範圍從10千帕((kPa))至3,000千帕，例如：從50千帕至2,300千帕，或從100千帕至1,500千帕。反應物饋入反應器的”蒸汽每小時空間速度”(GHSV)可為高於至少500/小時，例如：高於至少1,000/小時，高於至少2,500/小時，甚至高於至少5,000/小時。就範圍而言，GHSV可以從50/小時至50,000/小時，例如：從500/小時至30.000/小時，從1.000/小時至10.000/小時，或1,000/小時至6,500/小時。 The hydrogenation reaction can be carried out in the liquid phase or in the gas phase. Preferably, the reaction is carried out in the gas phase under the following conditions. The reaction temperature may range from 125 ° C to 350 ° C, for example, from 200 ° C to 325 ° C, from 225 ° C to 300 ° C, or from 250 ° C to 300 ° C. The pressure ranges from 10 kilopascals (kPa) to 3,000 kilopascals, for example, from 50 kilopascals to 2,300 kilopascals, or from 100 kilopascals to 1,500 kilopascals. The "vapor hourly space velocity" (GHSV) of the reactant feed to the reactor can be above at least 500/hour, for example: above at least 1,000/hour, above at least 2,500/hour, and even above at least 5,000/hour. In terms of ranges, GHSV can range from 50/hour to 50,000/hour, for example: from 500/hour to 30.000/hour, from 1.000/hour to 10.000/hour, or from 1,000/hour to 6,500/hour.

氫化可視情況選擇性地在選定蒸汽每小時空間速度((GHSV))下足以克服觸媒床壓降的壓力進行，雖然沒有限制使用較高的壓力，但應當理解在高空間速度((GHSV))，例如，5000/小時或6,500/小時通過反應器床，會遭遇到相當大的壓降。 The hydrogenation can optionally be carried out at a selected steam hourly space velocity ((GHSV)) sufficient to overcome the pressure of the catalyst bed pressure drop, although there is no limit to the use of higher pressures, but It will be appreciated that at high space velocity ((GHSV)), for example, 5000/hour or 6,500/hour, a considerable pressure drop is encountered through the reactor bed.

雖然反應每莫耳醋酸會消耗兩莫耳氫氣，而產生一莫耳的乙醇，在實際進料流中氫氣對醋酸的莫耳比可能會有所不同，可從100：1至1：100，例如，從50：1至1：50，從20：1至1：2，或從12：1至1：1。較佳者為，氫氣對醋酸的莫耳比高於2：1，例如高於4：1或高於8：1。 Although the reaction consumes two moles of hydrogen per mole of acetic acid to produce one mole of ethanol, the molar ratio of hydrogen to acetic acid in the actual feed stream may vary from 100:1 to 1:100. For example, from 50:1 to 1:50, from 20:1 to 1:2, or from 12:1 to 1:1. Preferably, the molar ratio of hydrogen to acetic acid is above 2:1, such as above 4:1 or above 8:1.

接觸或滯留時間也有很大的變動，其取決於醋酸量、觸媒、反應器、溫度和壓力等變數。典型的接觸時間範圍從低於1秒到數小時以上，若使用固定床以外的觸媒系統，則氣相反應較佳的接觸時間為從0.1秒至100秒，例如從0.3至80秒，或0.4秒至30秒。 There is also a large variation in contact or residence time, depending on the amount of acetic acid, catalyst, reactor, temperature and pressure. Typical contact times range from less than 1 second to more than a few hours. If a catalyst system other than a fixed bed is used, the preferred contact time for the gas phase reaction is from 0.1 second to 100 seconds, for example from 0.3 to 80 seconds, or 0.4 seconds to 30 seconds.

醋酸氫化形成乙醇較佳者為在氫化觸媒的存在下進行。合適的氫化觸媒包含金屬觸媒，其包含第一金屬和任意的一種或一種以上的第二金屬，第三金屬或任意的幾種其他金屬，隨意承載於觸媒支撐體上。第一金屬和隨意的第二金屬和第三金屬選自包含IB,IIB,IIIB,IVB,VB,VIB,VIIB,VIII族過渡金屬、鑭系金屬、錒系金屬之群組或選自IIIA,IVA,VA或VIA族之群組的任何金屬。一些典型觸媒組成物中較佳為的金屬組合包含鉑/錫、鉑/釕、鉑/錸、鈀/釕、鈀/錸、鈷/鈀、鈷/鉑、鈷/鉻、鈷/釕、鈷/錫、銀/鈀、銅/鈀、銅/鋅、鎳/鈀、金/鈀、釕/錸及釕/鐵。典型觸媒進一步記載於美國專利號第7,608,744號和第7,863,489號，與美國專利申請公開案號2010/0029995，其全部內容在此納入參考。在另一實施方式中，觸媒包含在美國專利申請公開案號2009/0069609描述的鈷/鉬/硫類型的觸媒，其全部內容在此納入參考。 Hydrogenation of acetic acid to form ethanol is preferably carried out in the presence of a hydrogenation catalyst. Suitable hydrogenation catalysts comprise a metal catalyst comprising a first metal and any one or more second metals, a third metal or any of several other metals, optionally supported on a catalyst support. The first metal and the optional second metal and third metal are selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, Group VIII transition metals, lanthanide metals, lanthanide metals or selected from IIIA. Any metal of the group of IVA, VA or VIA. Preferred metal combinations in some typical catalyst compositions include platinum/tin, platinum/rhodium, platinum/rhodium, palladium/ruthenium, palladium/iridium, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/ruthenium, Cobalt/tin, silver/palladium, copper/palladium, copper/zinc, nickel/palladium, gold/palladium, rhodium/iridium and bismuth/iron. Typical catalysts are further described in U.S. Patent Nos. 7,608,744 and 7, 863, 489, the disclosure of each of which is incorporated herein by reference. In another embodiment, the catalyst comprises a cobalt/molybdenum/sulfur type of catalyst as described in U.S. Patent Application Publication No. 2009/0069609, the entire disclosure of which is incorporated herein by reference.

在一實施方式中，觸媒包含第一金屬係選自由銅、鐵、鈷、鎳、釕、銠、鈀、鋨、銥、鉑、鈦、鋅、鉻、錸、鉬和鎢所組成之群組。較佳為第一金屬係選自由鉑、鈀、鈷、鎳和釕所組成之群組。更優選為第一金屬選自鉑和鈀。在本發明一實施方式中當第一金屬係鉑，較佳者為觸媒中鉑含量不超過5重量%，例如低於3重量%或低於1重量%，這是由於鉑的高商業需求而造成昂貴的價格所致。 In one embodiment, the catalyst comprises a first metal selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, lanthanum, molybdenum, and tungsten. group. Preferably, the first metal is selected from the group consisting of platinum, palladium, cobalt, nickel and ruthenium. More preferably, the first metal is selected from the group consisting of platinum and palladium. In an embodiment of the invention, when the first metal is platinum, preferably The platinum content in the catalyst does not exceed 5% by weight, such as less than 3% by weight or less than 1% by weight, which is due to the high commercial demand for platinum resulting in an expensive price.

如上所述，在一些實施方式中，該觸媒可視情況選擇性地的擇性地還包含第二金屬，其通常會作為一種促進劑。如果存在的話，第二金屬較佳者為選自由銅、鉬、錫、鉻、鐵、鈷、釩、鎢、鈀、鉑、鑭、鈰、錳、釕、錸、金及鎳所組成之群組。尤佳為，第二金屬係選自由銅、錫、鈷、錸及鎳所組成之群組。更佳者為，第二金屬選自錫及錸。 As noted above, in some embodiments, the catalyst optionally optionally further comprises a second metal, which typically acts as a promoter. If present, the second metal is preferably selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, rhodium, ruthenium, manganese, osmium, iridium, gold, and nickel. group. More preferably, the second metal is selected from the group consisting of copper, tin, cobalt, rhodium, and nickel. More preferably, the second metal is selected from the group consisting of tin and antimony.

如果觸媒包含兩種或更多種的金屬，例如第一金屬和第二金屬，則第一金屬用量可從0.1至10重量%，例如從0.1至5重量%，或從0.1至3重量%。第二金屬較佳的用量從0.1至20重量%，例如從0.1至10重量%，或者從0.1至5重量%。對於含兩種或兩種以上金屬的觸媒而言，兩種或更多種的金屬可以是可互為合金或可包含非合金之金屬溶液或混合物。 If the catalyst comprises two or more metals, such as a first metal and a second metal, the first metal may be used in an amount of from 0.1 to 10% by weight, such as from 0.1 to 5% by weight, or from 0.1 to 3% by weight. . The second metal is preferably used in an amount of from 0.1 to 20% by weight, for example from 0.1 to 10% by weight, or from 0.1 to 5% by weight. For a catalyst containing two or more metals, the two or more metals may be metal compounds or mixtures which may be alloys with each other or may comprise non-alloys.

較佳的金屬比例可能略有不同，取決於使用在觸媒中的金屬種類。在一些實施方式中，第一金屬對第二金屬的摩爾比較佳為10：1至1：10，例如：4：1至1：4，2：1至1：2，1.5：1至1：1.5，或1.1：1至1：1.1。 The preferred metal ratios may vary slightly depending on the type of metal used in the catalyst. In some embodiments, the molar ratio of the first metal to the second metal is preferably from 10:1 to 1:10, for example, from 4:1 to 1:4, from 2:1 to 1:2, from 1.5:1 to 1: 1.5, or 1.1:1 to 1:1.1.

觸媒亦可包含第三金屬，第三金屬可以選自上面列出的任何第一金屬或第二金屬，只要第三金屬不同於第一金屬和第二金屬即可。在較佳方面，第三金屬是選自由鈷、鈀、釕、銅、鋅、鉑、錫及錸所組成之群組。尤佳者為第三金屬選自鈷，鈀及釕。如果存在的話，第三金屬總重量在0.05至4重量%，例如：0.1至3重量%，或0.1至2重量%。 The catalyst may also comprise a third metal, which may be selected from any of the first or second metals listed above, as long as the third metal is different from the first metal and the second metal. In a preferred aspect, the third metal is selected from the group consisting of cobalt, palladium, rhodium, copper, zinc, platinum, tin, and antimony. More preferably, the third metal is selected from the group consisting of cobalt, palladium and rhodium. If present, the total weight of the third metal is from 0.05 to 4% by weight, for example from 0.1 to 3% by weight, or from 0.1 to 2% by weight.

除了一種或更多種的金屬外，在本發明一些實施方式中觸媒進一步包含支撐體或改質的支撐體。本文中所使用的“改質的支撐體”一詞指支撐體包含支撐體材料和支撐體改性劑(support modifier)，該改性劑係用來調節支撐體材料的酸度。 In addition to one or more metals, in some embodiments of the invention the catalyst further comprises a support or a modified support. As used herein, the term "modified support" means that the support comprises a support material and a support modifier for adjusting the acidity of the support material.

支撐體或改質的支撐體之總重量較佳者為觸媒總重量的75重量%至99.9重量%，例如：從78重量%至97重量%，或從80重量%至95重量%。在使用改質支撐體的較佳為的實施方式中例方式中，支撐體改性劑含量為觸媒總重量的0.1重量%至50重量%，例如：從0.2重量%至25重量%，由0.5重量%至15重量%，或從1%重量至8重量%。觸媒的金屬可分散在整個支撐體，塗層於整個支撐體，包覆在支撐體的外層(似蛋殼)或塗佈在支撐體的表面上。 The total weight of the support or modified support is preferably from 75% to 99.9% by weight of the total weight of the catalyst, for example from 78% to 97% by weight, or from 80% to 95% by weight. In a preferred embodiment of the preferred embodiment using a modified support, the support modifier content is from 0.1% by weight to 50% by weight based on the total weight of the catalyst, for example, from 0.2% by weight to 25% by weight, 0.5% by weight to 15% by weight, or from 1% by weight to 8% by weight. The metal of the catalyst can be dispersed throughout the support, coated over the entire support, coated on the outer layer of the support (like an eggshell) or coated on the surface of the support.

對此領域之熟悉技藝者即知選擇支撐體材料，使得該觸介質系在形成乙醇的製程條件下具有適當活性、選擇性和穩定強勁性(robust)。 Those skilled in the art will recognize that the support material is selected such that the contact medium has suitable activity, selectivity and stability robustness under the process conditions for forming ethanol.

適當的支撐體材料可包含，例如：穩定的金屬氧化物為基礎的支撐體或陶瓷系支撐體。較佳的支撐體包含含矽支撐體，例如二氧化矽、氧化矽/氧化鋁、IIA族矽酸鹽，例如偏矽酸鈣、熱解二氧化矽、高純度二氧化矽及其混合物。其他的支撐體，包含但不限於，氧化鐵、氧化鋁、二氧化鈦、氧化鋯、氧化鎂、碳、石墨、高表面積石墨化炭、活性炭及其混合物。 Suitable support materials may include, for example, a stable metal oxide based support or a ceramic support. Preferred supports comprise a ruthenium-containing support such as ruthenium dioxide, ruthenium oxide/alumina, Group IIA ruthenate such as calcium metasilicate, pyrogenic ruthenium dioxide, high purity ruthenium dioxide and mixtures thereof. Other supports include, but are not limited to, iron oxide, aluminum oxide, titanium dioxide, zirconium oxide, magnesium oxide, carbon, graphite, high surface area graphitized carbon, activated carbon, and mixtures thereof.

如所述，觸媒支撐體可能會被支撐體改性劑予以改質。在一些實施方式中，支撐體改性劑可能是酸性改性劑，其可增加觸媒的酸度。適用於酸性支撐體改性劑可以選自由IVB族金屬氧化物、VB族金屬氧化物、VIB族金屬氧化物、VIIB族金屬氧化物、VIIIB族金屬氧化物、氧化鋁和其混合物所組成之群組。酸性支撐體改性劑包含那些選自包含二氧化鈦、氧化鋯、氧化鈮、氧化鉭、氧化鋁、氧化硼、氧化磷和三氧化二銻所組成之群組。酸性支撐體改性劑包含那些係選自由二氧化鈦((TiO₂))、氧化鋯((ZrO₂))、氧化鈮((Nb₂O₅))、氧化鉭((Ta₂O₅))、氧化鋁((Al₂O₃))、氧化硼((B₂O₃))、五氧化二磷((P₂O₅))和三氧化二銻((Sb₂O₃))所組成之群組。較佳為的酸性支撐體改性劑包含那些係選自由二氧化鈦((TiO₂))、氧化鋯((ZrO₂))、氧化鈮((Nb₂O₅))、氧化鉭((Ta₂O₅))和氧化鋁 ((Al₂O₃))所組成之群組。酸性改性劑可能還包括氧化鎢((WO₃))、氧化鉬((MoO₃))、三氧化二鐵((Fe₂O₃))、三氧化二鉻((Cr₂O₃))、氧化釩((V₂O₅))、二氧化錳((MnO₂))、氧化銅((CuO))、氧化鈷((Co₂O₃))或氧化鉍((Bi₂O₃))。 As stated, the catalyst support may be modified by the support modifier. In some embodiments, the support modifier may be an acidic modifier that increases the acidity of the catalyst. Suitable for acidic support modifiers may be selected from the group consisting of Group IVB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIIIB metal oxides, aluminum oxides, and mixtures thereof. group. The acidic support modifiers include those selected from the group consisting of titanium dioxide, zirconium oxide, cerium oxide, cerium oxide, aluminum oxide, boron oxide, phosphorus oxide, and antimony trioxide. The acidic support modifiers include those selected from the group consisting of titanium dioxide ((TiO ₂ )), zirconium oxide ((ZrO ₂ )), cerium oxide ((Nb ₂ O ₅ )), cerium oxide ((Ta ₂ O ₅ )), Alumina ((Al ₂ O ₃ )), boron oxide ((B ₂ O ₃ )), phosphorus pentoxide ((P ₂ O ₅ )) and antimony trioxide ((Sb ₂ O ₃ )) Group. Preferred acidic support modifiers include those selected from the group consisting of titanium dioxide ((TiO ₂ )), zirconium oxide ((ZrO ₂ )), cerium oxide ((Nb ₂ O ₅ )), cerium oxide ((Ta ₂ O) ₅ )) and a group of alumina ((Al ₂ O ₃ )). The acid modifier may also include tungsten oxide ((WO ₃ )), molybdenum oxide ((MoO ₃ )), ferric oxide ((Fe ₂ O ₃ )), chromium oxide ((Cr ₂ O ₃ )) , vanadium oxide ((V ₂ O ₅ )), manganese dioxide ((MnO ₂ )), copper oxide ((CuO)), cobalt oxide ((Co ₂ O ₃ )) or cerium oxide ((Bi ₂ O ₃ ) ).

在另一實施方式中，支撐體改性劑可能是一種具有低揮發性或無揮發性的鹼性改性劑。此種的鹼性改性劑，例如，可以選自由：(i)鹼土金屬氧化物，(ii)鹼金屬氧化物，(iii)鹼土金屬偏矽酸鹽，(iv)鹼金屬偏矽酸鹽，(v)IIB族金屬氧化物，(vi)IIB族金屬偏矽酸鹽，(vii)IIIB族金屬氧化物，(viii)IIIB族金屬偏矽酸鹽，及其混合物所組成之群組。除氧化物和偏矽酸鹽外，其他類型的改性劑包含硝酸鹽、亞硝酸鹽、醋酸鹽和乳酸鹽亦可用。鹼性支撐體改性劑係選自由鈉、鉀、鎂、鈣、鈧、釔及鋅的氧化物和偏矽酸鹽，以及任何上述的混合物所組成之群組。較佳的支撐體改性劑是矽酸鈣，尤佳者為偏矽酸鈣((CaSiO₃))。如果支撐體改性劑包含偏矽酸鈣，較佳者為至少一部分的偏矽酸鈣呈結晶的形式。 In another embodiment, the support modifier may be an alkaline modifier with low or no volatility. Such a basic modifier, for example, may be selected from the group consisting of: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicate, (iv) an alkali metal metasilicate. a group of (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof. In addition to oxides and metasilicates, other types of modifiers including nitrates, nitrites, acetates and lactates can also be used. The alkaline support modifier is selected from the group consisting of oxides of sodium, potassium, magnesium, calcium, strontium, barium, and zinc and bismuth citrate, and mixtures of any of the foregoing. A preferred support modifier is calcium citrate, and more preferably calcium metasilicate ((CaSiO ₃ )). If the support modifier comprises calcium metasilicate, it is preferred that at least a portion of the calcium metasilicate is in crystalline form.

較佳的二氧化矽支撐體材料是SS61138高表面(HSA)的二氧化矽觸媒載體((Saint-Gobain NorPro公司))。此SS61138二氧化矽包含約95重量%的高表面積二氧化矽；表面積約250平方米/克；以汞擠入式孔隙分析儀測定得中位孔徑約12奈米(nm)，平均孔隙體積約1.0立方厘米/克；而反應器的反應器積密度約0.352公克/立方厘米(22磅/立方呎)。 A preferred ceria support material is SS61138 high surface (HSA) ceria catalyst carrier ((Saint-Gobain NorPro)). The SS61138 cerium oxide comprises about 95% by weight of high surface area cerium oxide; the surface area is about 250 square meters per gram; the median pore diameter is about 12 nanometers (nm) measured by a mercury extrusion pore analyzer, and the average pore volume is about 1.0 cubic centimeters per gram; and the reactor has a reactor density of about 0.352 grams per cubic centimeter (22 pounds per cubic foot).

較佳的氧化矽/氧化鋁支撐體材料是KA-160二氧化矽(Süd Chemie公司)，具有標稱直徑約5毫米，密度約0.562克/毫升，吸收度約0.583克水/克支撐體，表面積約160至175平方米/克，和孔隙體積約0.68毫升/克。 A preferred cerium oxide/alumina support material is KA-160 cerium oxide (Süd Chemie) having a nominal diameter of about 5 mm, a density of about 0.562 g/cc, and an absorbance of about 0.583 g water/g support. The surface area is about 160 to 175 square meters per gram, and the pore volume is about 0.68 milliliters per gram.

適合使用本發明的觸媒較佳為改性支撐體浸漬金屬而得，但其他製程，例如化學氣相沉積也可使用。此浸漬技術描述在美國專利號7,608,744和7,863,489，在此與美國專利申請公開案號2010/0197485，其全部內容在此納入參考。 The catalyst suitable for use in 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. This impregnation technique is described in U.S. Patent Nos. 7,608,744 and 7, 863, 489, the disclosure of which is incorporated herein by reference.

特別是，醋酸氫化可達成良好的醋酸轉化率和良好的對乙醇選擇率和產率。就本發明目的而言，“轉化率”是指在進料中的醋酸轉化成醋酸以外之化合物量。轉化率以在進料中醋酸之摩爾比例表示。轉化率至少可在10%以上，例如，至少有20%，至少有40%，至少有50%，至少有60%，至少有70%，或至少有80%。雖然觸媒具有較高的轉化率是可取的，例如轉化率至少有80%或至少有90%，但在一些實施方式中，若對乙醇有高選擇率，則較低的轉化率可以接受。這當然是很好理解的，在許多情況下，可以通過適當的循環流或使用更大的反應器，以彌補轉化率，但選擇率差則難以彌補。 In particular, hydrogenation of acetic acid achieves good acetic acid conversion and good selectivity to ethanol and yield. For the purposes of the present invention, "conversion" means the amount of a compound other than acetic acid converted to acetic acid in the feed. The conversion is expressed as the molar ratio of acetic acid in the feed. The conversion can be at least 10%, for example, at least 20%, at least 40%, at least 50%, at least 60%, at least 70%, or at least 80%. While it is desirable for the catalyst to have a higher conversion, such as a conversion of at least 80% or at least 90%, in some embodiments, a lower conversion is acceptable if there is a high selectivity to ethanol. This is of course well understood. In many cases, the conversion rate can be compensated by a suitable recycle stream or by using a larger reactor, but the difference in selectivity is difficult to compensate.

“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有獨立的選擇率，而選擇率也和轉化率無關。例如：如果60摩爾%的醋酸轉化為乙醇，我們指乙醇的選擇率為60%。較佳者為，觸媒對乙氧基化合物(ethoxylates)之選擇率至少有60%，例如：至少有70%，或至少有80%。本文中所使用的”乙氧基化合物”一詞，具體指乙醇、乙醛和醋酸乙酯。較佳者為乙醇的選擇率在80%以上，例如：至少有85%或至少有88%。在本發明實施方式中亦較佳者為，對不被期待的產物，例如甲烷、乙烷和二氧化碳有較低之選擇率。這些不被期待的產物的選擇率是低於4%，例如低於2%或低於1%。較佳者為在氫化製程中，未檢測到這些不被期待的產物。在一些本發明實施方式中，烷烴之形成率低，通常低於2%，往往低於1%，而且在許多情況下低於0.5%的醋酸通過觸媒轉化為烷烴，而烷烴除了作為燃料外並沒有多大價值。 "Selectivity" is expressed as mole percent of converted acetic acid. It should be recognized that each compound converted from acetic acid has an independent selectivity, and the selectivity is also independent of the conversion. For example, if 60 mole % of acetic acid is converted to ethanol, we mean that the selectivity of ethanol is 60%. Preferably, the catalyst has a selectivity to ethoxylates of at least 60%, for example at least 70%, or at least 80%. The term "ethoxylated compound" as used herein specifically refers to ethanol, acetaldehyde and ethyl acetate. Preferably, the selectivity for ethanol is above 80%, for example: at least 85% or at least 88%. It is also preferred in embodiments of the invention to have lower selectivity for undesirable products such as methane, ethane and carbon dioxide. The selectivity of these unanticipated products is less than 4%, such as less than 2% or less than 1%. Preferably, these undesired products are not detected during the hydrogenation process. In some embodiments of the invention, the formation rate of alkanes is low, typically less than 2%, often less than 1%, and in many cases less than 0.5% of the acetic acid is converted to alkanes by a catalyst, and the alkanes are used as fuel. It doesn't have much value.

“產率”是指氫化製程中每仟克觸媒每小時所形成特定的產物，例如乙醇，的克數。產率每仟克觸媒每小時至少有100克乙醇，例如：每仟克觸媒每小時至少有400克乙醇或較佳為至少有600克乙醇。以範圍而言，產率較佳為是每仟克觸媒每小時100至3,000克的乙醇，例如：400至2,500克或600至2,000克的乙醇。 "Yield" refers to the number of grams of a particular product, such as ethanol, formed per gram of catalyst per hour in the hydrogenation process. The yield is at least 100 grams of ethanol per gram of catalyst per hour, for example: at least 400 grams of ethanol per gram of catalyst per hour or preferably at least 600 grams of ethanol. In terms of range, the yield is preferably from 100 to 3,000 grams of ethanol per gram of catalyst per hour, for example: 400 to 2,500 grams or 600 to 2,000 grams of ethanol.

在本發明的條件下操作，可以使得乙醇生產的水平每小時至少0.1噸乙醇，例如：每小時至少有1噸乙醇，每小時至少有5噸乙醇，或每小時至少有10噸乙醇。較大規模的工業化生產乙醇，這取決於規模，一般應每小時至少有1噸乙醇，例如：每小時至少15噸乙醇或每小時至少30噸乙醇。就範圍而言，為大規模工業化生產乙醇，本發明製程每小時可產生從0.1至160噸的乙醇，例如：每小時從15至160噸乙醇或每小時從30至80噸乙醇。若藉由發酵來生產乙醇，由於經濟規模之考量，一般不適合採用本發明實施方式中方式所能達成的單一乙醇生產設施。 Operating under the conditions of the present invention, the level of ethanol production can be at least 0.1 tons of ethanol per hour, for example, at least 1 ton of ethanol per hour, at least 5 tons of ethanol per hour, or at least 10 tons of ethanol per hour. Larger scale industrial production of ethanol, depending on size, should generally have at least 1 ton of ethanol per hour, for example: at least 15 tons of ethanol per hour or at least 30 tons of ethanol per hour. In terms of scope, for large scale industrial production of ethanol, the process of the invention can produce from 0.1 to 160 tons of ethanol per hour, for example from 15 to 160 tons of ethanol per hour or from 30 to 80 tons of ethanol per hour. If ethanol is produced by fermentation, it is generally not suitable to employ a single ethanol production facility that can be achieved by the mode of the embodiment of the present invention due to economic scale considerations.

在各種本發明實施方式中，在任何後續處理，如純化和分離之前，氫化製程所生產的乙醇粗產物通常包含未反應的醋酸，乙醇和水。本文中所使用的“乙醇粗產物”一詞是指任何包含從5至70重量%的乙醇和5至40重量%的水之組成物。乙醇粗產物的典型組成範圍提供於表1。表1中定義的“其他”可以包含，例如：酯類、醚類、醛類、酮類、烷烴類和二氧化碳。 In various embodiments of the invention, the crude ethanol product produced by the hydrogenation process typically comprises unreacted acetic acid, ethanol and water prior to any subsequent processing, such as purification and separation. The term "ethanol crude product" as used herein refers to any composition comprising from 5 to 70% by weight of ethanol and from 5 to 40% by weight of water. A typical composition range of the crude ethanol product is provided in Table 1. "Others" as defined in Table 1 may include, for example, esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide.

在一實施方式中，乙醇粗產物包含醋酸，其量低於20重量%，例如：低於15重量%，低於10重量%或低於5重量%。在具有較低量醋酸的實施方式中，醋酸的轉化率較佳為高於75%，例如：高於85%，或高於90%。此外，乙醇之選擇率可也較佳者為高，其較佳者為高於75%，如高於85%或高於90%。 In one embodiment, the crude ethanol product comprises acetic acid in an amount less than 20% by weight, such as less than 15% by weight, less than 10% by weight or less than 5% by weight. In embodiments having a lower amount of acetic acid, the conversion of acetic acid is preferably greater than 75%, such as greater than 85%, or greater than 90%. In addition, the selectivity of ethanol may also be preferably higher, preferably greater than 75%, such as greater than 85% or greater than 90%.

乙醇回收Ethanol recovery

第1圖顯示根據本發明一實施方式的典型乙醇回收系統。根據本發明一實施方式，氫化系統100提供一個合適的氫化反應器，和從粗反應混合物分離乙醇的製程。系統100包括反應區101和分離區102。反應區101包括反應器103，氫氣進料管路104和醋酸進料管路105。分離區102包含包括分離器106，例如，閃蒸槽(flash vessel)及蒸餾塔。 Figure 1 shows a typical ethanol recovery system in accordance with an embodiment of the present invention. According to one embodiment of the invention, hydrogenation system 100 provides a suitable hydrogenation reactor and a process for separating ethanol from the crude reaction mixture. System 100 includes a reaction zone 101 and a separation zone 102. Reaction zone 101 includes reactor 103, hydrogen feed line 104, and acetic acid feed line 105. The separation zone 102 includes a separator 106, such as a flash vessel and a distillation column.

氫氣和烷酸(較佳者為醋酸)分別經由管路104和105輸送到蒸發器109，而在管路110建立蒸汽進料流，其導向反應器103。在一實施方式中，管路104和管路105可結合，並共同送入蒸發器109。較佳者為在管路110的蒸汽進流溫度是從100℃至350℃間，例如，從120℃至310℃，或150℃至300℃。任何未蒸發的進料是從蒸發器109移出，並可以予以再循環或廢棄之。此外，雖然如所示管路110導向反應器103的頂部，但是管路110亦可導向反應器的側邊，上部或底部。下面描述反應區101和分離區102的進一步修改和其他額外的組件。 Hydrogen and alkanoic acid (preferably acetic acid) are delivered to evaporator 109 via lines 104 and 105, respectively, and a vapor feed stream is established in line 110 which is directed to reactor 103. In one embodiment, the line 104 and the line 105 can be combined and fed together into the evaporator 109. Preferably, the vapor influent temperature in line 110 is from 100 ° C to 350 ° C, for example, from 120 ° C to 310 ° C, or from 150 ° C to 300 ° C. Any unvaporized feed is removed from evaporator 109 and can be recycled or discarded. In addition, although the line 110 is directed to the reaction as shown The top of the vessel 103, but the line 110 can also be directed to the side, upper or bottom of the reactor. Further modifications and other additional components of reaction zone 101 and separation zone 102 are described below.

反應器103含有用於氫化烷酸(較佳者為醋酸)之觸媒。在一實施方式中，一張或多張保護床(未顯示)可用於反應器的上游，可視情況選擇性地於蒸發器109的上游，以防止觸媒接觸到含於進料或返回/循環流中的毒物或不良雜質。這樣的保護床可用於蒸汽流或液體流。適合保護床材料可包含，例如：碳、二氧化矽、氧化鋁、陶瓷或樹脂。在一方面，保護床介質加以官能化(functionalized)，例如銀官能化，以捕獲特定的物種，如硫或鹵素。在氫化製程中，較佳者為不斷地從反應器103通過管路111取出乙醇粗產物。 Reactor 103 contains a catalyst for hydrogenating an alkanoic acid, preferably acetic acid. In one embodiment, one or more guard beds (not shown) may be used upstream of the reactor, optionally upstream of the evaporator 109, to prevent contact of the catalyst with feed or return/cycle Toxic or undesirable impurities in the stream. Such a guard bed can be used for a steam stream or a liquid stream. Suitable guard bed materials may include, for example, carbon, cerium oxide, aluminum oxide, ceramics or resins. In one aspect, the guard bed media is functionalized, such as silver functionalized, to capture a particular species, such as sulfur or a halogen. In the hydrogenation process, it is preferred to continuously withdraw the crude ethanol product from reactor 103 through line 111.

乙醇粗產物流可加以冷凝和輸送到分離器106，其又會轉而提供蒸汽流112和液體流113。在一些實施方式中，分離器106可包括閃蒸塔或分液釜(knockout pot)。分離器106操作溫度可從20℃至250℃，例如，從30℃至225℃，或60℃至200℃。分離器106的壓力可從50千帕至2,000千帕，例如，從75千帕至1,500 kPa，或100千帕到1,000千帕。可視情況選擇性地，在管路111的粗乙醇產物可以通過一張或多張分離膜，以分離氫氣和/或其他非可冷凝性氣體。 The ethanol crude product stream can be condensed and sent to a separator 106, which in turn provides a vapor stream 112 and a liquid stream 113. In some embodiments, the separator 106 can include a flash column or a knockout pot. The separator 106 can operate at a temperature of from 20 ° C to 250 ° C, for example, from 30 ° C to 225 ° C, or from 60 ° C to 200 ° C. The pressure of the separator 106 can range from 50 kPa to 2,000 kPa, for example, from 75 kPa to 1,500 kPa, or from 100 kPa to 1,000 kPa. Optionally, the crude ethanol product in line 111 may pass through one or more separation membranes to separate hydrogen and/or other non-condensable gases.

排出分離器106的蒸汽流112包含氫氣和碳氫化合物，可以加以吹氣清除和/或返回到反應區101。如上所示，蒸汽流112結合氫氣進料104，並共同饋入蒸發器109。在一些實施方式中，返回的蒸汽流112在結合氫氣進料104之前可予以壓縮。 The vapor stream 112 exiting the separator 106 contains hydrogen and hydrocarbons which may be purged off and/or returned to the reaction zone 101. As indicated above, the vapor stream 112 incorporates the hydrogen feed 104 and is fed into the evaporator 109 in common. In some embodiments, the returned steam stream 112 can be compressed prior to combining the hydrogen feed 104.

抽移來自分離器106的液體流113，作為進料組成物導入第一蒸餾塔107側邊，而第一蒸餾塔也稱為“輕餾份蒸餾塔”。在一實施方式中，液體流113內容大致類似於從反應器所獲得之乙醇粗產物，只除了組成物中已除盡氫氣、二氧化碳、甲烷或乙烷，因其等已被分離器106所移除。因此，液體流113也可被稱為乙醇粗產物。表2中提供液體流 113的典型成分。應當理解液體流113可包含未列於表2的其他成分，例如衍生自進料的成分。 The liquid stream 113 from the separator 106 is pumped as a feed composition to the side of the first distillation column 107, and the first distillation column is also referred to as a "light fraction distillation column". In one embodiment, the liquid stream 113 content is substantially similar to the crude ethanol product obtained from the reactor except that hydrogen, carbon dioxide, methane or ethane has been removed from the composition as it has been removed by the separator 106. except. Thus, liquid stream 113 can also be referred to as a crude ethanol product. Liquid flow is provided in Table 2 Typical composition of 113. It should be understood that liquid stream 113 may comprise other components not listed in Table 2, such as components derived from the feed.

在整份申請書表中低於(<)顯示的量較佳為不存在，如果存在的話，僅僅可能存在微量，或高於0.0001重量%。 The amount shown below (<) in the entire application form is preferably absent, if present, only trace amounts may be present, or greater than 0.0001% by weight.

表2中“其他酯類”可以包含但不限於，丙酸乙酯、醋酸甲酯、醋酸異丙酯、醋酸正丙酯、醋酸丁酯或其混合物。表2中”其他醚類”可以包含但不限於，***、甲基乙基醚、異丁基乙基醚或其混合物。表2中”其他醇類”可以包含但不限於，甲醇、異丙醇、正丙醇、正丁醇或其混合物。在一實施方式中，液體流113可包含丙醇、例如異丙醇和/或正丙醇，其含量從0.001到0.1重量%，從0.001到0.05重量%或0.001到0.03重量%。應該了解，這些其他成分可以藉由這裡所述任何餾出物或殘留物流携帶之，除非特別註明，本文不會再進一步描述。 The "other esters" in Table 2 may include, but are not limited to, ethyl propionate, methyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate or a mixture thereof. The "other ethers" in Table 2 may include, but are not limited to, diethyl ether, methyl ethyl ether, isobutyl ethyl ether or a mixture thereof. The "other alcohols" in Table 2 may include, but are not limited to, methanol, isopropanol, n-propanol, n-butanol or a mixture thereof. In one embodiment, liquid stream 113 may comprise propanol, such as isopropanol and/or n-propanol, in an amount from 0.001 to 0.1% by weight, from 0.001 to 0.05% by weight or from 0.001 to 0.03% by weight. It should be understood that these other ingredients may be carried by any of the distillates or residual streams described herein and will not be further described herein unless otherwise noted.

可視情況選擇性地，在管路111之乙醇粗產物或液體流113可進一步送入酯化反應器，氫解反應器，或兩者兼而有之。酯化反應器可用於消耗存在於乙醇粗產物之醋酸，而進一步減少欲移除之醋酸量。氫解可以用來轉化乙醇粗產物中之醋酸乙酯，而產生乙醇。 Optionally, the crude ethanol or liquid stream 113 in line 111 can be further fed to an esterification reactor, a hydrogenolysis reactor, or both. Esterification reactor can be used The acetic acid present in the crude ethanol product is consumed to further reduce the amount of acetic acid to be removed. Hydrogenolysis can be used to convert ethyl acetate in the crude ethanol product to produce ethanol.

在第1圖所示的實施方式中，液體流113引入第一蒸餾塔107的上部，例如，上半部或更高的上面三分之一處。在一實施方式中，沒有夾帶劑添加到第一蒸餾塔107。在第一蒸餾塔107中，主要量的乙醇、水、醋酸、和其他重餾份，如果存在的話，較佳者為從液體流113中不斷地被抽移，作為管路114中的殘留物。第一蒸餾塔107也形成塔頂餾出物，其由管路115抽移，並可予以濃縮和回流，例如，以回流比從30：1至1：30，例如，從10：1至1：10，或從1：5至5：1回流之。較佳者為在物流115之塔頂餾出物包含來自液體流113中主要量的醋酸乙酯和乙醛。有益的是，小量的，例如，至少0.1重量ppm，至少1重量ppm，至少10重量ppm，至少有100重量ppm，或至少1,000重量ppm的醋酸乙酯和/或乙醛，單獨或集體，允許通過進入第一殘留物，因為下面所討論的第二蒸餾塔會提供一種手段，其可有效地從產物乙醇組成物去除這些化合物的殘留量。 In the embodiment shown in Figure 1, liquid stream 113 is introduced into the upper portion of first distillation column 107, for example, in the upper third or higher upper third. In one embodiment, no entrainer is added to the first distillation column 107. In the first distillation column 107, a major amount of ethanol, water, acetic acid, and other heavy fractions, if any, are preferably continuously withdrawn from the liquid stream 113 as a residue in the line 114. . The first distillation column 107 also forms an overhead which is pumped by line 115 and which can be concentrated and refluxed, for example, at a reflux ratio of from 30:1 to 1:30, for example, from 10:1 to 1 :10, or reflow from 1:5 to 5:1. Preferably, the overhead product at stream 115 comprises a major amount of ethyl acetate and acetaldehyde from liquid stream 113. Desirably, for example, at least 0.1 ppm by weight, at least 1 ppm by weight, at least 10 ppm by weight, at least 100 ppm by weight, or at least 1,000 ppm by weight of ethyl acetate and/or acetaldehyde, alone or collectively, Passing through the first residue is permitted because the second distillation column discussed below provides a means to effectively remove residual amounts of these compounds from the product ethanol composition.

當蒸餾塔107在約170千帕壓力下操作時，在管路114排出的殘留物溫度較佳者為從70℃至155℃，例如，從90℃至130℃，或從100℃至110℃。蒸餾塔107的底部可藉由抽移包含乙醇、水和醋酸之殘留物流，而維持在一相對的低溫度，從而提供能源效率的優勢。在蒸餾塔107管路115排出的餾出溫度，在170千帕壓力時，較佳者為從75℃至100℃，例如，從75℃至83℃，或從81℃至84℃。在一些實施方式中，第一蒸餾塔107的壓力範圍可從0.1千帕至510千帕，例如，從1千帕至475千帕，或1千帕至375千帕。在下面的表3提供第一蒸餾塔107餾出物和殘留物的典型成分。應該也可以理解餾出物和殘留物也可包含未列於表3中的其他成分。為方便起見，第一蒸餾塔的餾出物和殘留物也可被稱為"第一餾出物”或"第一殘留物”。其他蒸餾塔的餾出物或殘留物也可具有類似數字修飾語((第二，第三等等))，以區分彼此，但這樣的修飾語不應被解釋為要求任何特定的分離順序。 When the distillation column 107 is operated at a pressure of about 170 kPa, the temperature of the residue discharged in the line 114 is preferably from 70 ° C to 155 ° C, for example, from 90 ° C to 130 ° C, or from 100 ° C to 110 ° C. . The bottom of distillation column 107 can be maintained at a relatively low temperature by pumping a residual stream comprising ethanol, water and acetic acid to provide an energy efficiency advantage. The distillation temperature discharged in the line 115 of the distillation column 107 is preferably from 75 ° C to 100 ° C, for example, from 75 ° C to 83 ° C, or from 81 ° C to 84 ° C at a pressure of 170 kPa. In some embodiments, the pressure of the first distillation column 107 can range from 0.1 kPa to 510 kPa, for example, from 1 kPa to 475 kPa, or from 1 kPa to 375 kPa. Typical compositions of the first distillation column 107 distillate and residue are provided in Table 3 below. It should also be understood that the distillate and residue may also contain other ingredients not listed in Table 3. For convenience, the distillate and residue of the first distillation column may also be referred to as "first distillate" or "first residue." Other distillation tower The distillate or residue may also have similar numerical modifiers ((second, third, etc.)) to distinguish one another, but such modifiers should not be construed as requiring any particular order of separation.

在本發明實施方式中，可調節蒸餾塔107操作的溫度，使得大部分的水、乙醇、及醋酸都是從殘留物流中移除，而只有少量乙醇和水收集在餾出物中，由於形成的二元共沸物和三元共沸物。在管路114殘留物中的水對在管路115餾出物中的水之重量比高於1：1，例如高於2：1。在殘留物中的乙醇對在餾出物中的乙醇之重量比高於1：1，例如高於2：1。在管路115第一餾出物中的醋酸乙酯對在管路114第一殘留物中的醋酸乙酯之重量比可高於1：1，例如高於2：1。在管路115第一餾出物中的乙醛對在管路114第一殘留物中的乙醛之重量比可高於1：1，例如高於2：1。 In an embodiment of the invention, the temperature at which the distillation column 107 is operated can be adjusted such that most of the water, ethanol, and acetic acid are removed from the residual stream, while only a small amount of ethanol and water are collected in the distillate due to formation. Binary azeotrope and ternary azeotrope. The weight ratio of water in the residue of line 114 to water in the distillate of line 115 is above 1:1, such as above 2:1. The weight ratio of ethanol to residual ethanol in the residue is above 1:1, such as above 2:1. The weight ratio of ethyl acetate to the ethyl acetate in the first residue of line 114 in the first distillate of line 115 can be above 1:1, such as above 2:1. The weight ratio of acetaldehyde to acetaldehyde in the first residue of line 114 in the first distillate of line 115 can be above 1:1, such as above 2:1.

在第一殘留物114的醋酸量可能會有所不同，主要取決於反應器103的轉化率。在一實施方式中，當轉化率高時，例如，高於90%，則醋酸在第一殘留物中之量可低於10重量%，例如低於5重量%或低於2重量%。在其他實施方式中，當轉化率較低時，例如低於90%，則醋酸在第一殘留物中之量可高於10重量%。 The amount of acetic acid in the first residue 114 may vary, depending primarily on the conversion of the reactor 103. In one embodiment, when the conversion is high, for example, greater than 90%, the amount of acetic acid in the first residue may be less than 10% by weight, such as less than 5% by weight or less than 2% by weight. In other embodiments, when the conversion is low, such as less than 90%, the amount of acetic acid in the first residue can be greater than 10% by weight.

在第一蒸餾塔107中的分離可用或不用共沸物或萃取劑而進行之。 The separation in the first distillation column 107 can be carried out with or without an azeotrope or an extractant.

第一餾出物較佳者為實質上不含醋酸，例如，包含低於1,000 ppm，低於500ppm，或低於100 ppm的醋酸。餾出物可從系統中加以吹氣清除，或者全部或部分再循環回到反應器103。在一些實施方式中，餾出物可以進一步分離，例如，在蒸餾塔(未顯示)分離成為乙醛流和醋酸乙酯流。這兩支物流可送回反應器103或系統100作為一種單獨的產物。 The first distillate is preferably substantially free of acetic acid, for example, containing less than 1,000 ppm, less than 500 ppm, or less than 100 ppm of acetic acid. The distillate can be purged from the system by blowing or recycled, in whole or in part, to reactor 103. In some embodiments, the distillate can be further separated, for example, in a distillation column (not shown) to separate into an acetaldehyde stream and an ethyl acetate stream. These two streams can be returned to reactor 103 or system 100 as a separate product.

在一實施方式中，在此並沒有顯示出來，使全部或部分的第一餾出物導入水解裝置，在其中所含的醋酸乙酯與水反應生成乙醇和醋酸，這兩者都可再循環回到反應器或送到分離系統以回收之。因此，在一實施方式中，製程包括在水解裝置水解至少一部分的第一餾出物，而形成包含乙醇和醋酸之水解產物，並使至少一部分的水解產物導入反應器或分離系統，例如第一蒸餾塔或第二蒸餾塔。在另一方面，不經水解，而將全部或部分的第一餾出物再循環回到反應器。 In one embodiment, it is not shown here that all or part of the first distillate is introduced into the hydrolysis unit, and the ethyl acetate contained therein reacts with water to form ethanol and acetic acid, both of which are recyclable. Return to the reactor or send it to a separation system for recycling. Thus, in one embodiment, the process includes hydrolyzing at least a portion of the first distillate in the hydrolysis unit to form a hydrolysate comprising ethanol and acetic acid, and introducing at least a portion of the hydrolyzate into the reactor or separation system, such as first a distillation column or a second distillation column. In another aspect, all or a portion of the first distillate is recycled back to the reactor without hydrolysis.

一些例如縮醛類的物種可在第一蒸餾塔107分解，使得在餾出物或殘留物中縮醛含量很低，甚至檢測不到縮醛類。 Some species such as acetals may be decomposed in the first distillation column 107 such that the acetal content is very low in the distillate or residue, and even the acetals are not detected.

此外，乙醇粗產物從反應器103排出後，在乙醇粗產物中可能會發生醋酸/乙醇和醋酸乙酯之間的平衡反應。根據醋酸在乙醇粗產物中的濃度，這種平衡可趨向醋酸乙酯的形成。這種反應是可以通過粗乙醇產物的滯留時間和/或溫度來調節之。 Further, after the crude ethanol product is discharged from the reactor 103, an equilibrium reaction between acetic acid/ethanol and ethyl acetate may occur in the crude ethanol product. This equilibrium may tend to form ethyl acetate depending on the concentration of acetic acid in the crude ethanol product. This reaction can be adjusted by the residence time and/or temperature of the crude ethanol product.

第1圖所顯示的蒸餾塔可包括具有能夠執行所欲的分離和/或純化功能之任何蒸餾塔。較佳者為每一蒸餾塔係一種塔盤式蒸餾塔，具有從1 至150個塔盤，例如，從10至100個塔盤，從20至95個塔盤，或從30至75個塔盤。塔盤可為篩盤、固定閥塔盤、移動閥塔盤或具有文獻上已知的任何其他合適的設計。在其他實施方式中，可以使用填充式蒸餾塔。就填充式蒸餾塔而言，規整填料和零散填料均可使用。這些塔盤或填料可安排在一連續的蒸餾塔，或者也可以安排在兩座或更多座的蒸餾塔，使得當蒸氣從第一段進入第二段之同時，液體從第二段進入第一段等等。 The distillation column shown in Figure 1 can include any distillation column having the ability to perform the desired separation and/or purification functions. Preferably, each distillation column is a tray distillation column having from 1 Up to 150 trays, for example, from 10 to 100 trays, from 20 to 95 trays, or from 30 to 75 trays. The tray can be a sieve tray, a fixed valve tray, a moving valve tray or any other suitable design known in the literature. In other embodiments, a packed distillation column can be used. In the case of a packed distillation column, both structured packing and loose packing can be used. These trays or packings may be arranged in a continuous distillation column or may be arranged in two or more distillation columns so that when the vapor enters the second stage from the first stage, the liquid enters the second stage from the second stage. One paragraph and so on.

配用於每一蒸餾塔的相關冷凝器和液體分離槽可以是任何傳統的設計，並簡化於圖中。通過熱交換器或再沸器(reboiler)，可以提供熱量給每蒸餾塔底部，或提供熱量給循環中的底部流。也可使用其他類型的再沸器，如內部再沸器。提供再沸器的熱量可來自任何製程中生成的熱量，該製程可和再沸器整合在一起或配用外部熱源，如其他發熱化學製程或鍋爐之外部熱源。雖然如圖所示只具一反應器和一閃蒸塔，但是在本發明各種實施方式中可以用附加的反應器、閃蒸塔、冷凝器、加熱元件和其他元件。對此領域之熟悉技藝者即知通常採用化學製程之各種冷凝器、泵、壓縮機、再沸器、轉筒、閥門、連接器、分離容器等，也可進行合併並整合在一起使用於本發明的製程中。 The associated condenser and liquid separation tanks associated with each distillation column can be of any conventional design and are simplified in the drawings. Heat can be supplied to the bottom of each distillation column through a heat exchanger or reboiler, or heat can be supplied to the bottom stream in the cycle. Other types of reboilers, such as internal reboilers, can also be used. The heat supplied to the reboiler can be derived from the heat generated in any process, and the process can be integrated with the reboiler or with an external heat source such as other heating chemical processes or external heat sources of the boiler. Although only one reactor and one flash column are shown as shown, additional reactors, flash towers, condensers, heating elements, and other components may be utilized in various embodiments of the invention. Those skilled in the art will recognize that various condensers, pumps, compressors, reboilers, drums, valves, connectors, separation vessels, etc., which are commonly used in chemical processes, may also be combined and integrated for use in this field. In the process of the invention.

用於諸蒸餾塔的溫度和壓力可以有所變動。作為一個實際問題，通常在這些區域可採用從10千帕至3,000千帕的壓力，雖然在一些實施方式中，次大氣壓力或超大氣壓力的壓力均可採用。不同區域內的溫度一般介於移出之餾出物組成物的沸點和移出之殘留物組成物的沸點之間。對所屬技術領域中具有通常知識者即知在操作蒸餾塔某一點的溫度是端賴於在該位置的物料組成和蒸餾塔內壓力。此外，視生產製程的規模而定，進料速率可以有所不同，如果加以描述的話，可籠統地以進料重量比率表示。 The temperatures and pressures used in the distillation columns can vary. As a practical matter, a pressure of from 10 kPa to 3,000 kPa is usually employed in these regions, although in some embodiments, subatmospheric pressure or superatmospheric pressure may be employed. The temperature in the different zones is generally between the boiling point of the removed distillate composition and the boiling point of the removed residue composition. It is known to those of ordinary skill in the art that the temperature at a point in the operation of the distillation column depends on the composition of the material at that location and the pressure in the distillation column. In addition, depending on the scale of the manufacturing process, the feed rate can vary and, if described, can be expressed generally in terms of feed weight ratio.

為回收乙醇，在管路114的殘留物可進一步分離，其係根據醋酸、水和/或醋酸乙酯的濃度而定。在本發明中大部分的實施方式中，在管路 114的殘留物進一步在第二蒸餾塔119分離。在第1圖中，第二蒸餾塔119被稱為"酸分離蒸餾塔"，因為第二殘留物122包含醋酸和水。例如，當在第一殘留物的醋酸濃度高於1重量%，像是高於5重量%時，是可以使用酸分離蒸餾塔的。 To recover the ethanol, the residue in line 114 can be further separated depending on the concentration of acetic acid, water and/or ethyl acetate. In most embodiments of the invention, in the pipeline The residue of 114 is further separated in the second distillation column 119. In Fig. 1, the second distillation column 119 is referred to as an "acid separation distillation column" because the second residue 122 contains acetic acid and water. For example, when the acetic acid concentration in the first residue is more than 1% by weight, such as more than 5% by weight, it is possible to use an acid separation distillation column.

在第1圖中，管路114的第一殘留物引入到第二蒸餾塔119，例如，酸分離蒸餾塔，較佳者為引入點在蒸餾塔119的頂部，例如，上半部或更高的上面三分之一處。第二蒸餾塔119產生在管路122包含醋酸和水的第二殘留物，在管路120中包含殘留醋酸乙酯和/或殘留乙醛的第二餾出物，以及包含乙醇的乙醇側流121。藉由在側流產生產物乙醇，而分離水、醋酸和殘留醋酸乙酯，本發明提供一種低能源的解決方案，可視情況選擇性地只有兩座蒸餾塔，即可從乙醇粗產物回收乙醇。第二蒸餾塔119可以是一種塔盤式蒸餾塔或填充式蒸餾塔。在一實施方式中，第二蒸餾塔119是一種塔盤式蒸餾塔，其具有從5至150個塔盤，如從15至50個塔盤或從20至45個塔盤。雖然第二蒸餾塔119的溫度和壓力可能會有所不同，但是在大氣壓力下由第二蒸餾塔119管路122排出的第二殘留物溫度較佳者為從95℃至130℃，例如，從100℃至125℃或110℃至120℃。從第二蒸餾塔119管路120排出的第二餾出物溫度較佳者為從60℃至105℃，例如，從75℃至100℃，或80℃至100℃。在管路121排出的乙醇側流溫度較佳者為從60℃至105℃，例如，從75℃至100℃，或80℃至100℃。第二蒸餾塔119壓力範圍可從0.1千帕至510千帕，例如，從1千帕至475千帕或1千帕至375千帕。第二蒸餾塔119的餾出物和殘留物之典型成分提供於下面的表4。應當理解餾出物和殘留物也可能包含未列於表4中之其他成分，例如來自進料的成分。 In Fig. 1, the first residue of line 114 is introduced to a second distillation column 119, such as an acid separation distillation column, preferably at the top of distillation column 119, for example, the upper half or higher. Above the third. The second distillation column 119 produces a second residue comprising acetic acid and water in line 122, a second distillate containing residual ethyl acetate and/or residual acetaldehyde in line 120, and an ethanol side stream comprising ethanol. 121. By separating the water, acetic acid and residual ethyl acetate by producing the product ethanol in a side stream, the present invention provides a low energy solution, optionally with only two distillation columns, to recover ethanol from the crude ethanol product. The second distillation column 119 may be a tray distillation column or a packed distillation column. In one embodiment, the second distillation column 119 is a tray distillation column having from 5 to 150 trays, such as from 15 to 50 trays or from 20 to 45 trays. Although the temperature and pressure of the second distillation column 119 may vary, the temperature of the second residue discharged from the second distillation column 119 line 122 at atmospheric pressure is preferably from 95 ° C to 130 ° C, for example, From 100 ° C to 125 ° C or 110 ° C to 120 ° C. The temperature of the second distillate discharged from the second distillation column 119 line 120 is preferably from 60 ° C to 105 ° C, for example, from 75 ° C to 100 ° C, or from 80 ° C to 100 ° C. The temperature of the ethanol side stream discharged in the line 121 is preferably from 60 ° C to 105 ° C, for example, from 75 ° C to 100 ° C, or from 80 ° C to 100 ° C. The second distillation column 119 may have a pressure ranging from 0.1 kPa to 510 kPa, for example, from 1 kPa to 475 kPa or 1 kPa to 375 kPa. Typical components of the distillate and residue of the second distillation column 119 are provided in Table 4 below. It should be understood that the distillate and residue may also contain other ingredients not listed in Table 4, such as ingredients from the feed.

在管路121側流中乙醇對在管路122第二殘留物中乙醇的比較佳者為至少2：1，至少10：1，或至少35：1。在一實施方式中，在第二殘留物122的水對在第二餾出物120的水之比高於2：1，例如高於4：1，或高於6：1。此外，在第二殘留物122的醋酸對在第二餾出物120的醋酸之比較佳者為高於10：1，例如高於15：1，或高於20：1。較佳者為，在管路120的第二餾出物和側流121實質上不含醋酸，若有的話，可能只包含極微量的醋酸。在管路120及管路121的醋酸濃度降低有利於提供不含醋酸或只包含極微量醋酸的乙醇產物。此外，如上所述，本分離流程的優點是能夠在兩座蒸餾塔系統有效地從產物乙醇去除醋酸乙酯。在一實施方式中，管路120第二餾出物中醋酸乙酯對管路121側流中醋酸乙酯的比高於2：1，高於5：1，或高於10：1。 Preferably, the ethanol in the side stream of line 121 is at least 2:1, at least 10:1, or at least 35:1, in the second residue of line 122. In one embodiment, the ratio of the water pair in the second residue 122 to the water in the second distillate 120 is above 2:1, such as above 4:1, or above 6:1. Further, the acetic acid in the second residue 122 is preferably higher than 10:1, such as higher than 15:1, or higher than 20:1, in the second distillate 120. Preferably, the second distillate and side stream 121 in line 120 are substantially free of acetic acid and, if any, may contain only a minor trace of acetic acid. The reduced concentration of acetic acid in line 120 and line 121 facilitates the supply of an ethanol product that does not contain acetic acid or contains only a very small amount of acetic acid. Furthermore, as described above, the separation process has the advantage of being able to effectively remove from the product ethanol in the two distillation column systems. Ethyl acetate. In one embodiment, the ratio of ethyl acetate in the second distillate of line 120 to the ethyl acetate in the side stream of line 121 is greater than 2:1, above 5:1, or above 10:1.

管路118的第二餾出物可從系統中加以吹氣清除，或者全部或部分和管路115的第一餾出物一起再循環回到反應器103。 The second distillate of line 118 can be purged from the system or recycled, in whole or in part, with the first distillate of line 115 back to reactor 103.

管路122的第二殘留物包含醋酸和水。根據含於第二殘留物中水和醋酸的量，可採用一種或多種以下方法來處理殘留物。以下是進一步處理殘留物的典型方法，應當理解不管酸的濃度如何，任一(或無)以下方法可以使用。若殘留物包含大部分，例如高於70重量%，的醋酸，則殘留物可再循環回到反應器，而不必做任何的水分離。在一實施方式中，若殘留物包含主要量，例如高於50重量%，的醋酸，則可分離殘留物成為醋酸流和水性物流。在一些實施方式中，醋酸也可以從酸濃度較低的殘留物回收。藉由蒸餾塔或一種或多種分離膜可將殘留物分離成為醋酸和水性物流。如果分離膜或分離膜陣列組用於從水中分離醋酸，則分離膜或分離膜陣列組可以選自任何能夠移除滲透水性物流的合適耐酸分離膜。所獲得之醋酸流可選擇性地返回到反應區。所獲得之水性物流可用來作為萃取劑或在水解裝置中水解含酯流，例如水解全部或部分的第一餾出物115，如上所述。 The second residue of line 122 contains acetic acid and water. Depending on the amount of water and acetic acid contained in the second residue, one or more of the following methods may be employed to treat the residue. The following is a typical method for further processing of the residue, it being understood that any (or none) of the following methods can be used regardless of the acid concentration. If the residue contains a large portion, for example more than 70% by weight of acetic acid, the residue can be recycled back to the reactor without any water separation. In one embodiment, if the residue comprises a major amount, such as greater than 50% by weight of acetic acid, the residue can be separated into an acetic acid stream and an aqueous stream. In some embodiments, acetic acid can also be recovered from residues having a lower acid concentration. The residue can be separated into acetic acid and an aqueous stream by a distillation column or one or more separation membranes. If the separation membrane or separation membrane array set is used to separate acetic acid from water, the separation membrane or separation membrane array set may be selected from any suitable acid-resistant separation membrane capable of removing the permeate aqueous stream. The acetic acid stream obtained can be selectively returned to the reaction zone. The aqueous stream obtained can be used as an extractant or to hydrolyze an ester-containing stream in a hydrolysis unit, for example to hydrolyze all or part of the first distillate 115, as described above.

在其他實施方式中，例如，在第二殘留物包含低於50重量%的酸，可能的選項包括一種或多種：(i)返回部分殘留物到反應器103，(ii)中和酸，(iii)使乙醇和酸反應，或(iv)將殘留物排放於廢水處理設施處理。也可使用弱酸性的回收蒸餾塔分離包括低於50重量%醋酸的殘留物，在蒸餾塔中加入溶劑(可視情況選擇性地作為共沸劑)。適合作此用途的典型溶劑可包括醋酸乙酯、醋酸丙酯、醋酸異丙酯、醋酸丁酯、醋酸乙烯酯、二異丙醚、二硫化碳、四氫呋喃、異丙醇、乙醇、及C₃-C₁₂的烷烴。中和醋酸時，較佳者為殘留物包含低於10重量%的醋酸。醋酸可用任何合適的鹼金屬或鹼土金屬鹼，例如氫氧化鈉或氫氧化鉀，中和之。當醋酸與乙醇反應時，較佳為殘留物包括低於50 重量%之酸。醇可以是任何合適的醇，例如甲醇、乙醇、丙醇、丁醇、或其混合物。形成酯之反應可與其他系統，例如羰基化生產或酯生產製程整合在一起。較佳者為，醇包括乙醇，而所獲得之酯包括醋酸乙酯。可視情況選擇性地，所獲得之酯可送入氫化反應器。 In other embodiments, for example, where the second residue comprises less than 50% by weight acid, possible options include one or more of: (i) returning a portion of the residue to reactor 103, (ii) neutralizing the acid, ( Iii) reacting the ethanol with the acid, or (iv) discharging the residue to a wastewater treatment facility. It is also possible to separate the residue comprising less than 50% by weight of acetic acid using a weakly acidic recovery distillation column, and to add a solvent (optionally as an entrainer as the case may be) in the distillation column. Typical solvents suitable for this purpose may include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, vinyl acetate, diisopropyl ether, carbon disulfide, tetrahydrofuran, isopropanol, ethanol, and C ₃ -C ₁₂ alkane. When neutralizing acetic acid, it is preferred that the residue contain less than 10% by weight of acetic acid. The acetic acid can be neutralized with any suitable alkali or alkaline earth metal base such as sodium hydroxide or potassium hydroxide. When acetic acid is reacted with ethanol, it is preferred that the residue comprises less than 50% by weight of acid. The alcohol can be any suitable alcohol such as methanol, ethanol, propanol, butanol, or mixtures thereof. The ester forming reaction can be combined with other systems, such as carbonylation production or ester production processes. Preferably, the alcohol comprises ethanol and the ester obtained comprises ethyl acetate. Optionally, the ester obtained can be fed to a hydrogenation reactor.

在一些實施方式中，若第二殘留物包含極少量，例如，低於5重量%，之醋酸，則第二殘留物不必進一步處理可直接排放於廢水處理設施。有益的是殘留物的有機內容物，例如殘留物的醋酸，可適合用在廢水處理設施中餵養微生物。 In some embodiments, if the second residue comprises a very small amount, for example, less than 5% by weight of acetic acid, the second residue can be directly discharged to the wastewater treatment facility without further processing. Advantageously, the organic content of the residue, such as the acetic acid of the residue, may be suitable for feeding microorganisms in a wastewater treatment facility.

根據水濃度，乙醇產物可來自管路121的側流。在一方面，在管路121的側流包含至少88重量%的乙醇，至少90重量%的乙醇，至少95重量%的乙醇，或至少97重量%的乙醇。在一實施方式中，在管路121的側流可包含從75至96重量%的乙醇和低於12重量%的水。一些應用，例如工業乙醇的應用，可以容忍水存在乙醇產物之中，而其他應用，例如燃料應用，則需要無水乙醇。在管路121中側流的水含量可接近共沸量的水，例如至少有4重量%，較佳者為低於20重量%，例如低於12重量%，或低於7.5重量%。藉由幾種不同的分離技術，水可視情況選擇性地從管路121側流予以移除。去除殘留的水可藉由，例如一種或多種吸附裝置、分離膜、分子篩、萃取蒸餾裝置、或其組合而完成之。合適的吸附裝置包括壓變吸附系統及熱變吸附裝置。特別優先考慮的技術包括使用蒸餾塔、分離膜、吸附裝置及其組合。例如，來自第二蒸餾塔之側流可在一座額外的蒸餾塔蒸餾，形成包含乙醇的額外餾出物，和包含水的額外殘留物。 The ethanol product may come from a side stream of line 121 depending on the water concentration. In one aspect, the side stream in line 121 comprises at least 88% by weight ethanol, at least 90% by weight ethanol, at least 95% by weight ethanol, or at least 97% by weight ethanol. In an embodiment, the side stream at line 121 may comprise from 75 to 96% by weight ethanol and less than 12% by weight water. Some applications, such as industrial ethanol, can tolerate the presence of water in the ethanol product, while other applications, such as fuel applications, require anhydrous ethanol. The water content in the side stream in line 121 may be close to the azeotropic amount of water, for example at least 4% by weight, preferably less than 20% by weight, such as less than 12% by weight, or less than 7.5% by weight. Water can be selectively removed from the sidestream of line 121 by several different separation techniques. Removal of residual water can be accomplished by, for example, one or more adsorption devices, separation membranes, molecular sieves, extractive distillation devices, or combinations thereof. Suitable adsorption devices include pressure swing adsorption systems and thermal adsorption adsorption devices. Particularly preferred techniques include the use of distillation columns, separation membranes, adsorption devices, and combinations thereof. For example, the side stream from the second distillation column can be distilled in an additional distillation column to form an additional distillate comprising ethanol, and an additional residue comprising water.

如第1圖所示，可提供吸附裝置123從管路121側流移除水性物流125的水，於是產生無水乙醇流124，其較佳者為包含97重量%或更多的乙醇，例如，至少98重量%的乙醇，或至少99.5重量%的乙醇。吸附裝置123可採用合適的吸附劑，例如沸石。在一較佳的實施方式中，吸附裝置123是一種壓變吸附(PSA)裝置，其操作溫度從30℃至 160℃，例如，從80℃至140℃，而操作壓力從0.01千帕至550千帕，例如，從1至150千帕。PSA裝置可包括兩張到五張吸附床。吸附裝置123可從管路121側流移除至少95%的水，較佳者為從管路121側流移除95%至99.9%的水。水性物流125可與系統100中任何其他水性物流組合，可從系統中移除，或使用於其他系統，例如，作為一種水解第一餾出物中醋酸乙酯之水解劑。水性物流也可包括乙醇，在這種情況下，可能需要將全部或部分的水性物流饋回到第一蒸餾塔107或其他分離裝置，以便進一步回收乙醇。 As shown in FIG. 1, the adsorption device 123 can be provided to remove water from the aqueous stream 125 from the side of the line 121, thus producing an anhydrous ethanol stream 124, preferably containing 97% by weight or more of ethanol, for example, At least 98% by weight of ethanol, or at least 99.5% by weight of ethanol. The adsorption unit 123 may employ a suitable adsorbent such as zeolite. In a preferred embodiment, the adsorption device 123 is a pressure swing adsorption (PSA) device operating at temperatures ranging from 30 ° C to 160 ° C, for example, from 80 ° C to 140 ° C, and operating pressures from 0.01 kPa to 550 kPa, for example, from 1 to 150 kPa. The PSA unit can include two to five adsorbent beds. The adsorption unit 123 can remove at least 95% of the water from the side of the line 121, preferably 95% to 99.9% of the water removed from the side of the line 121. The aqueous stream 125 can be combined with any other aqueous stream in the system 100, can be removed from the system, or used in other systems, for example, as a hydrolyzing agent that hydrolyzes ethyl acetate in the first distillate. The aqueous stream may also include ethanol, in which case it may be desirable to feed all or part of the aqueous stream back to the first distillation column 107 or other separation unit for further recovery of the ethanol.

本發明的製程中所產生的乙醇產物可以是工業級乙醇，其包含從75至96重量%的乙醇，例如，從80到96重量%，從85到96重量%的乙醇，該百分率係對乙醇產物總重量而言。完成之乙醇典型組成範圍提供下面表5。 The ethanol product produced in the process of the present invention may be a technical grade ethanol comprising from 75 to 96% by weight of ethanol, for example from 80 to 96% by weight, from 85 to 96% by weight of ethanol, the percentage being ethanol In terms of the total weight of the product. The typical composition range of the completed ethanol is provided in Table 5 below.

本發明的完成之乙醇組成物較佳者為包含非常低量，例如低於0.5重量%，的其他醇類，像是甲醇、正丁醇、異丁醇、異戊醇及其C₄-C₂₀醇。在一實施方式中，完成之乙醇組成物量中異丙醇的含量是從80至1,000重量ppm，例如，從95至1,000重量ppm，100至700重量 ppm，或從150至500重量ppm。在一實施方式中，完成之乙醇組成物實質上不含乙醛，可視情況選擇性地包含低於8重量ppm的乙醛，例如低於5重量ppm，或低於1重量ppm的乙醛。 The finished ethanol composition of the present invention preferably comprises other alcohols such as methanol, n-butanol, isobutanol, isoamyl alcohol and C ₄ -C thereof in a very low amount, for example less than 0.5% by weight. ₂₀ alcohol. In one embodiment, the amount of isopropanol in the finished ethanol composition is from 80 to 1,000 ppm by weight, for example, from 95 to 1,000 ppm by weight, from 100 to 700 ppm by weight, or from 150 to 500 ppm by weight. In one embodiment, the finished ethanol composition is substantially free of acetaldehyde, optionally containing less than 8 ppm by weight of acetaldehyde, such as less than 5 ppm by weight, or less than 1 ppm by weight of acetaldehyde.

本發明實施方式完成之乙醇組成物適合使用在多種應用，包含燃料、溶劑、化工原料、藥品、清潔劑、消毒劑、氫化傳送或消費品。在燃料應用，完成之乙醇組成物可與汽油混合用於機動運載工具，如汽車、船隻和小型活塞式發動機飛機。在非燃料應用上，完成之乙醇組成物可用作化妝品和美容製劑之溶劑、洗滌劑、消毒劑、塗料、油墨、和藥品。完成之乙醇組成物還可以用作製程溶劑，其可供醫藥產品、食品製劑、染料、光化學和乳膠加工之用。 The ethanol composition completed in the embodiments of the present invention is suitable for use in a variety of applications, including fuels, solvents, chemical materials, pharmaceuticals, detergents, disinfectants, hydrogenated delivery or consumer products. In fuel applications, the finished ethanol composition can be blended with gasoline for use in motor vehicles such as automobiles, boats and small piston engine aircraft. In non-fuel applications, the finished ethanol composition can be used as a solvent, detergent, disinfectant, coating, ink, and pharmaceutical for cosmetic and cosmetic preparations. The finished ethanol composition can also be used as a process solvent for pharmaceutical products, food preparations, dyes, photochemicals, and latex processing.

完成之乙醇組成物還可以用作化學原料，製造其他化學材料，如醋、丙烯酸乙酯、醋酸乙酯、乙烯、乙二醇醚類、乙胺類、醛類、高級醇類，尤其是丁醇。在生產醋酸乙酯中，完成之乙醇組成物可藉由醋酸進行酯化。在另一個應用中，完成之乙醇組成物可脫水生產乙烯。任何已知的脫水觸媒可以用來使乙醇脫水，如描述於美國專利申請公開案號2010/0030002和2010/0030001，其全部內容及揭露在此納入參考。沸石觸媒，例如，可用為脫水觸媒。較佳者為沸石具有孔隙直徑至少有0.6奈米，較佳之沸石包含脫水觸媒，其選自包含絲光沸石、ZSM-5、沸石X和沸石Y之群組。X型沸石，例如：描述於美國專利第2,882,244號和Y型沸石描述於美國專利第3,130,007號，其全部內容在此納入參考。 The completed ethanol composition can also be used as a chemical raw material to make other chemical materials such as vinegar, ethyl acrylate, ethyl acetate, ethylene, glycol ethers, ethylamines, aldehydes, higher alcohols, especially alcohol. In the production of ethyl acetate, the finished ethanol composition can be esterified by acetic acid. In another application, the finished ethanol composition can be dehydrated to produce ethylene. Any of the known dehydration catalysts can be used to dehydrate the ethanol, as described in U.S. Patent Application Publication Nos. 2010/0030002 and 2010/0030001, the entire contents of which are incorporated herein by reference. The zeolite catalyst, for example, can be used as a dehydration catalyst. Preferably, the zeolite has a pore diameter of at least 0.6 nm. Preferably, the zeolite comprises a dehydration catalyst selected from the group consisting of mordenite, ZSM-5, zeolite X and zeolite Y. X-type zeolites are described, for example, in U.S. Patent No. 2,882,244, and Y-type zeolites are described in U.S. Patent No. 3,130,007, the entire disclosure of which is incorporated herein by reference.

雖然本發明已詳細描述，但在本發明精義和範圍內之各種修改對所屬領域之熟悉技藝者而言係顯而易見。以上討論相關的知識和技術文獻的背景及詳細說明，其中揭露均可在此納入參考。此外，還應該認識到本發明層面和各實施方式的部分和以下各種特色和/或所附申請專利範圍，是可以合併或互換全部或部分。在前面各種實施方式的描述中，提到的另一種實施方式可以適當結合其他實施方式，對所屬領域之熟悉技藝者將能理解。再者，那些知悉普通的技術文獻者都明白前面描述只是舉例說明，不是為了限制本發明保護範圍。 While the invention has been described in detail, the various modifications and The background and detailed description of the relevant knowledge and technical literature are discussed above, the disclosure of which is incorporated herein by reference. In addition, it should be understood that the aspects of the present invention and the various embodiments and the various features and/or the scope of the appended claims may be combined or interchanged in whole or in part. In the foregoing description of various embodiments, another embodiment mentioned may be combined with other embodiments as appropriate, and is familiar with the art. Artists will be able to understand. Furthermore, those skilled in the art will understand that the foregoing description is only illustrative and not intended to limit the scope of the invention.

100‧‧‧氫化系統 100‧‧‧Hydrogenation system

101‧‧‧反應區 101‧‧‧Reaction zone

102‧‧‧分離區 102‧‧‧Separation zone

103‧‧‧反應器 103‧‧‧Reactor

104‧‧‧氫氣進料管路/管路 104‧‧‧Hydrogen feed line/pipe

105‧‧‧醋酸進料管路/管路 105‧‧‧Acetic acid feed line/pipe

106‧‧‧分離器 106‧‧‧Separator

107‧‧‧第一蒸餾塔/輕餾份蒸餾塔 107‧‧‧First Distillation Tower/Light Distillation Distillation Tower

109‧‧‧蒸發器 109‧‧‧Evaporator

110‧‧‧管路 110‧‧‧pipe

111‧‧‧管路 111‧‧‧pipe

112‧‧‧蒸汽流 112‧‧‧Steam flow

113‧‧‧液體流 113‧‧‧Liquid flow

114‧‧‧管路/第一殘留物 114‧‧‧pipe/first residue

115‧‧‧管路/物流/第一餾出物 115‧‧‧Line/Logistics/First Distillate

118‧‧‧管路 118‧‧‧ pipeline

119‧‧‧第二蒸餾塔/蒸餾塔 119‧‧‧Second distillation tower/distillation tower

120‧‧‧管路 120‧‧‧pipe

121‧‧‧乙醇側流 121‧‧‧Ethanol sidestream

122‧‧‧管路/第二殘留物 122‧‧‧pipe/second residue

123‧‧‧吸附裝置 123‧‧‧Adsorption device

124‧‧‧無水乙醇流 124‧‧‧ Anhydrous ethanol stream

125‧‧‧水性物流 125‧‧‧Water Logistics

以下參考圖式詳細解說本發明各種實施方式，更可完全地理解本發明。 The invention will be more fully understood from the following detailed description of embodiments of the invention.

第1圖係按照本發明一實施方式藉由兩座分離蒸餾塔回收乙醇之乙醇生產系統示意圖。 Fig. 1 is a schematic view showing an ethanol production system for recovering ethanol by two separation distillation columns according to an embodiment of the present invention.

100‧‧‧氫化系統 100‧‧‧Hydrogenation system

101‧‧‧反應區 101‧‧‧Reaction zone

102‧‧‧分離區 102‧‧‧Separation zone

103‧‧‧反應器 103‧‧‧Reactor

104‧‧‧氫氣進料管路/管路 104‧‧‧Hydrogen feed line/pipe

105‧‧‧醋酸進料管路/管路 105‧‧‧Acetic acid feed line/pipe

106‧‧‧分離器 106‧‧‧Separator

109‧‧‧蒸發器 109‧‧‧Evaporator

110‧‧‧管路 110‧‧‧pipe

111‧‧‧管路 111‧‧‧pipe

112‧‧‧蒸汽流 112‧‧‧Steam flow

113‧‧‧液體流 113‧‧‧Liquid flow

114‧‧‧管路/第一殘留物 114‧‧‧pipe/first residue

118‧‧‧管路 118‧‧‧ pipeline

120‧‧‧管路 120‧‧‧pipe

121‧‧‧乙醇側流 121‧‧‧Ethanol sidestream

122‧‧‧管路/第二殘留物 122‧‧‧pipe/second residue

123‧‧‧吸附裝置 123‧‧‧Adsorption device

124‧‧‧無水乙醇流 124‧‧‧ Anhydrous ethanol stream

125‧‧‧水性物流 125‧‧‧Water Logistics

Claims

一種用於生產乙醇的製程，包括以下步驟：(a)在反應器中觸媒的存在下，氫化醋酸而形成乙醇粗產物；(b)在第一蒸餾塔分離至少一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇的第一殘留物；及(c)在第二蒸餾塔從至少一部分的第一殘留物回收乙醇側流。 A process for producing ethanol comprising the steps of: (a) hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product; (b) separating at least a portion of the crude ethanol product in the first distillation column, and Producing a first distillate comprising ethyl acetate, and a first residue comprising ethanol; and (c) recovering an ethanol side stream from at least a portion of the first residue in the second distillation column.

如申請專利範圍第1項所述之製程，其中乙醇側流包含至少50重量%的乙醇。 The process of claim 1, wherein the ethanol side stream comprises at least 50% by weight of ethanol.

如申請專利範圍第1項所述之製程，其中乙醇側流包含至少88重量%的乙醇。 The process of claim 1, wherein the ethanol side stream comprises at least 88% by weight of ethanol.

如申請專利範圍第1項所述之製程，其中第二蒸餾塔也形成包含至少有1重量%醋酸乙酯的第二餾出物。 The process of claim 1, wherein the second distillation column also forms a second distillate comprising at least 1% by weight ethyl acetate.

如申請專利範圍第1項所述之製程，其中第二蒸餾塔也形成包含至少5重量%醋酸乙酯的第二餾出物。 The process of claim 1, wherein the second distillation column also forms a second distillate comprising at least 5% by weight ethyl acetate.

如申請專利範圍第1項所述之製程，其中第二蒸餾塔也形成包含至少5重量%醋酸乙酯的第二餾出物，且製程還包括使至少一部分的第二餾出物再循環回到反應器。 The process of claim 1, wherein the second distillation column also forms a second distillate comprising at least 5% by weight ethyl acetate, and the process further comprises recycling at least a portion of the second distillate back To the reactor.

如申請專利範圍第1項所述之製程，還包括進一步將至少一部分的第一餾出物送回到反應器。 The process of claim 1, further comprising further feeding at least a portion of the first distillate back to the reactor.

如申請專利範圍第1項所述之製程，還包括在水解裝置中水解一部分的第一餾出物而形成包含乙醇和醋酸的水解產物。 The process of claim 1, further comprising hydrolyzing a portion of the first distillate in the hydrolysis unit to form a hydrolysate comprising ethanol and acetic acid.

如申請專利範圍第1項所述之製程，還包括在水解裝置中水解一部分的第一餾出物而形成包含乙醇和醋酸的水解產物，並將至少一部分的水解產物導向反應器。 The process of claim 1, further comprising hydrolyzing a portion of the first distillate in the hydrolysis unit to form a hydrolysate comprising ethanol and acetic acid, and directing at least a portion of the hydrolyzate to the reactor.

如申請專利範圍第1項所述之製程，還包括與至少一部分係衍生自水解裝置中第二殘留物的水，來水解至少一部分的第一餾出物而形成包含乙醇和醋酸的水解產物。 The process of claim 1, further comprising hydrolyzing at least a portion of the first distillate derived from the second residue in the hydrolysis unit to hydrolyze at least a portion of the first distillate to form a hydrolysate comprising ethanol and acetic acid.

如申請專利範圍第1項所述之製程，還包括使至少一部分的第一餾出物再循環回到反應器。 The process of claim 1, further comprising recycling at least a portion of the first distillate back to the reactor.

如申請專利範圍第1項所述之製程，其中第二蒸餾塔也形成包含水和醋酸的第二殘留物。 The process of claim 1, wherein the second distillation column also forms a second residue comprising water and acetic acid.

如申請專利範圍第1項所述之製程，其中第二蒸餾塔也形成至少有1重量%醋酸乙酯的第二餾出物，和包含水和醋酸的第二殘留物。 The process of claim 1, wherein the second distillation column also forms a second distillate having at least 1% by weight of ethyl acetate, and a second residue comprising water and acetic acid.

如申請專利範圍第1項所述之製程，其中乙醇粗產物中之乙醇至少有70%移除於第一殘留物流中。 The process of claim 1, wherein at least 70% of the ethanol in the crude ethanol product is removed from the first residue stream.

如申請專利範圍第1項所述之製程，其中第一殘留物包含10至75重量%的乙醇，0.01至35重量%的醋酸，及25至70重量%的水。 The process of claim 1, wherein the first residue comprises 10 to 75% by weight of ethanol, 0.01 to 35% by weight of acetic acid, and 25 to 70% by weight of water.

如申請專利範圍第1項所述之製程，其中第一餾出物包含10至85重量%的醋酸乙酯，0.1至70重量%的乙醛，低於55重量%的乙醇，以及低於20重量%的水。 The process of claim 1, wherein the first distillate comprises 10 to 85% by weight of ethyl acetate, 0.1 to 70% by weight of acetaldehyde, less than 55% by weight of ethanol, and less than 20%. % by weight of water.

如申請專利範圍第1項所述之製程，還包括減少側流的含水量而產生含水量降低的乙醇產物流。 The process of claim 1, further comprising reducing the water content of the side stream to produce a reduced water product ethanol product stream.

如申請專利範圍第1項所述之製程，其中側流包含75至96重量%的乙醇，低於12重量%的水，低於1重量%的醋酸，和低於5重量%的醋酸乙酯。 The process of claim 1, wherein the side stream comprises 75 to 96% by weight of ethanol, less than 12% by weight of water, less than 1% by weight of acetic acid, and less than 5% by weight of ethyl acetate. .

如申請專利範圍第1項所述之製程，其中側流包含低於1重量%的醋酸乙酯。 The process of claim 1, wherein the side stream comprises less than 1% by weight of ethyl acetate.

如申請專利範圍第1項所述之製程，其中側流包含低於3重量%的水。 The process of claim 1, wherein the side stream comprises less than 3% by weight water.

如申請專利範圍第1項所述之製程，還包括藉由分離膜分離至少一部分的側流，而產生包含水的滲透流，和包含乙醇以及包含較該至少一部分的側流為少之水的截留流。 The process of claim 1, further comprising separating at least a portion of the side stream by the separation membrane to produce a permeate stream comprising water, and comprising less ethanol than the at least a portion of the side stream. Intercept the flow.

如申請專利範圍第1項所述之製程，還包括藉由一種或多種萃取劑萃取至少一部分的側流，而產生水含量降低之乙醇產物流。 The process of claim 1, further comprising extracting at least a portion of the side stream by one or more extractants to produce a reduced water product ethanol product stream.

如申請專利範圍第1項所述之製程，其中醋酸由甲醇和一氧化碳反應形成，其中用於氫化之每一甲醇、一氧化碳和氫氣均衍生自合成氣，而該合成氣是得自碳源係選自由天然氣、原油、石油、煤炭、生物料、及其組合所組成之群組。 The process of claim 1, wherein the acetic acid is formed by the reaction of methanol and carbon monoxide, wherein each of the methanol, carbon monoxide and hydrogen used for hydrogenation is derived from syngas, and the syngas is selected from the carbon source. A group of free natural gas, crude oil, petroleum, coal, biomass, and combinations thereof.

一種用於生產乙醇的製程，包括以下步驟：(a)提供包含乙醇和醋酸乙酯的乙醇粗產物；(b)在第一蒸餾塔分離至少一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇產量的第一殘留物；及(c)在第二蒸餾塔從至少一部分的第一殘留物回收乙醇側流。 A process for producing ethanol comprising the steps of: (a) providing a crude ethanol product comprising ethanol and ethyl acetate; and (b) separating at least a portion of the crude ethanol product in the first distillation column to produce ethyl acetate. a first distillate, and a first residue comprising ethanol production; and (c) recovering an ethanol side stream from at least a portion of the first residue in the second distillation column.

一種用於生產乙醇的製程，包括以下步驟：在反應器中觸媒的存在下，氫化醋酸而形成乙醇粗產物；在第一蒸餾塔分離至少一部分的乙醇粗產物而產生包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸及水的第一殘留物，其中送入第一蒸餾塔之乙醇粗產物中大部分的乙醇移除於第一殘留物中；及在第二蒸餾塔分離至少一部分的第一殘留物，而產生包含乙醇的側流，和包含水和殘餘醋酸的第二殘留物。 A process for producing ethanol, comprising the steps of: hydrogenating acetic acid to form a crude ethanol product in the presence of a catalyst in a reactor; and separating at least a portion of the crude ethanol product in the first distillation column to produce a product comprising ethyl acetate a distillate, and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol fed to the first distillation column is removed from the first residue; and is separated in the second distillation column At least a portion of the first residue produces a side stream comprising ethanol, and a second residue comprising water and residual acetic acid.

如申請專利範圍第25項所述之製程，其中在乙醇粗產物中至少有70%的乙醇移除於第一殘留物流中。 The process of claim 25, wherein at least 70% of the ethanol in the crude ethanol product is removed from the first residue stream.

如申請專利範圍第25項所述之製程，其中由第一蒸餾塔排出的第一殘留物溫度從70至155℃。 The process of claim 25, wherein the first residue discharged from the first distillation column has a temperature of from 70 to 155 °C.

如申請專利範圍第25項所述之製程，其中第一殘留物包含10至75重量%的乙醇、0.01至35重量%的醋酸、和25至70重量%的水。 The process of claim 25, wherein the first residue comprises 10 to 75% by weight of ethanol, 0.01 to 35% by weight of acetic acid, and 25 to 70% by weight of water.

如申請專利範圍第25項所述之製程，其中第一餾出物包含10至85重量%的醋酸乙酯、0.1至70重量%的乙醛、低於55重量%的乙醇、和低於20重量%的水。 The process of claim 25, wherein the first distillate comprises 10 to 85% by weight of ethyl acetate, 0.1 to 70% by weight of acetaldehyde, less than 55% by weight of ethanol, and less than 20 % by weight of water.

如申請專利範圍第25項所述之製程，還包括將至少一部分的第一餾出物送回到反應器。 The process of claim 25, further comprising feeding at least a portion of the first distillate back to the reactor.

如申請專利範圍第25項所述之製程，還包括在水解裝置水解至少一部分的第一餾出物，而形成包含乙醇和醋酸的水解產物。 The process of claim 25, further comprising hydrolyzing at least a portion of the first distillate in the hydrolysis unit to form a hydrolysate comprising ethanol and acetic acid.

如申請專利範圍第25項所述之製程，還包括在水解裝置水解至少一部分的第一餾出物，而形成包含乙醇和醋酸的水解產物，並將至少一部分的水解產物導入反應器。 The process of claim 25, further comprising hydrolyzing at least a portion of the first distillate in the hydrolysis unit to form a hydrolysate comprising ethanol and acetic acid, and introducing at least a portion of the hydrolyzate into the reactor.

如申請專利範圍第25項所述之製程，還包括與至少一部分係衍生自水解裝置中第二殘留物的水，來水解至少一部分的第一餾出物，而形成包含乙醇和醋酸的水解產物。 The process of claim 25, further comprising hydrolyzing at least a portion of the first distillate derived from the second residue in the hydrolysis unit to hydrolyze at least a portion of the first distillate to form a hydrolysate comprising ethanol and acetic acid. .

如申請專利範圍第25項所述之製程，還包括將至少一部分的第一餾出物再循環回到反應器。 The process of claim 25, further comprising recycling at least a portion of the first distillate back to the reactor.

如申請專利範圍第25項所述之製程，其中在第一殘留物的乙醇對在第一餾出物的乙醇之重量比至少是1：1。 The process of claim 25, wherein the weight ratio of the ethanol pair in the first residue to the ethanol in the first distillate is at least 1:1.

如申請專利範圍第25項所述之製程，其中第二蒸餾塔形成包含殘留醋酸乙酯的第二餾出物。 The process of claim 25, wherein the second distillation column forms a second distillate comprising residual ethyl acetate.

如申請專利範圍第25項所述之製程，其中側流包含75至96重量%的乙醇、低於12重量%的水、低於1重量%的醋酸、及低於5重量%的醋酸乙酯。 The process of claim 25, wherein the side stream comprises 75 to 96% by weight of ethanol, less than 12% by weight of water, less than 1% by weight of acetic acid, and less than 5% by weight of ethyl acetate. .

如申請專利範圍第25項所述之製程，還包括減少側流含水量，而產生含水量降低的乙醇產物流。 The process of claim 25, further comprising reducing the sidestream water content to produce a reduced water product ethanol product stream.

如申請專利範圍第38項所述之製程，其中乙醇產物流包含低於1重量%的醋酸乙酯。 The process of claim 38, wherein the ethanol product stream comprises less than 1% by weight ethyl acetate.

如申請專利範圍第38項所述之製程，其中乙醇產物流包含低於3重量%的水。 The process of claim 38, wherein the ethanol product stream comprises less than 3% by weight water.

如申請專利範圍第25項所述之製程，還包括藉由分離膜分離至少一部分的側流，而形成包含水的滲透流，和包含乙醇以及包含較該至少一部分的側流為少之水的截留流。 The process of claim 25, further comprising separating at least a portion of the side stream by the separation membrane to form a permeate stream comprising water, and comprising less ethanol than the at least a portion of the side stream. Intercept the flow.

如申請專利範圍第25項所述之製程，還包括藉由一種或多種萃取劑萃取至少一部分的側流，而產生水含量降低的乙醇產物流。 The process of claim 25, further comprising extracting at least a portion of the side stream by one or more extractants to produce a reduced water product ethanol product stream.

如申請專利範圍第25項所述之製程，其中醋酸由甲醇和一氧化碳反應形成，其中用於氫化步驟之甲醇、一氧化碳和氫氣均係各自衍生自合成氣，而其中該合成氣是衍生自碳源，其係選自由天然氣、原油、石油、煤炭、生物料、及其組合所組成之群組。 The process of claim 25, wherein the acetic acid is formed by the reaction of methanol and carbon monoxide, wherein the methanol, carbon monoxide and hydrogen used in the hydrogenation step are each derived from a synthesis gas, wherein the synthesis gas is derived from a carbon source. It is selected from the group consisting of natural gas, crude oil, petroleum, coal, biomass, and combinations thereof.

一種用於生產乙醇的製程，包括以下步驟：(a)提供乙醇粗產物；(b)在第一蒸餾塔分離一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸、和水的第一殘留物，其中使送入第一蒸餾塔的乙醇粗產物中大部分之乙醇移除於第一殘留物中；及(c)在第二蒸餾塔中分離至少一部分的第一殘留物，而產生包含乙醇的側流，和包含水和殘餘醋酸的第二殘留物。 A process for producing ethanol comprising the steps of: (a) providing a crude ethanol product; (b) separating a portion of the crude ethanol product in a first distillation column to produce a first distillate comprising ethyl acetate, and comprising a first residue of ethanol, acetic acid, and water, wherein a majority of the ethanol in the crude ethanol product fed to the first distillation column is removed from the first residue; and (c) is separated in the second distillation column A portion of the first residue produces a side stream comprising ethanol and a second residue comprising water and residual acetic acid.

一種用於生產乙醇的製程，包括以下步驟：(a)在反應器中觸媒的存在下氫化醋酸，而形成乙醇粗產物；(b)在第一蒸餾塔分離一部分的乙醇粗產物，而產生包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸和水的第一殘留物，其中送入蒸餾塔的乙醇粗產物中大部分的乙醇，移除於第一殘留物；及(c)在第二蒸餾塔中分離至少一部分的第一殘留物，而產生包括殘留醋酸乙酯的第二餾出物，和包含乙醇的側流。 A process for producing ethanol, comprising the steps of: (a) hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product; (b) separating a portion of the crude ethanol product in the first distillation column to produce a first distillate comprising ethyl acetate, and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the crude ethanol product fed to the distillation column is removed from the first residue; and (c At least a portion of the first residue is separated in the second distillation column to produce a second distillate comprising residual ethyl acetate, and a side stream comprising ethanol.

一種用於生產乙醇的製程，包括以下步驟：提供包含乙醇、醋酸乙酯、水、及醋酸之乙醇粗產物；在第一蒸餾塔分離一部分的乙醇粗產物，而形成包含醋酸乙酯的第一餾出物，和包含乙醇、醋酸和水的第一殘留物，其中將送到蒸餾塔的乙醇粗產物中大部分的乙醇移除於第一殘留物；及在第二蒸餾塔分離至少一部分的第一殘留物，而產生包含殘留醋酸乙酯的第二餾出物，和包括乙醇的側流。 A process for producing ethanol, comprising the steps of: providing a crude ethanol product comprising ethanol, ethyl acetate, water, and acetic acid; separating a portion of the crude ethanol product in the first distillation column to form a first product comprising ethyl acetate a distillate, and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the crude ethanol product sent to the distillation column is removed from the first residue; and at least a portion is separated in the second distillation column The first residue produces a second distillate comprising residual ethyl acetate, and a side stream comprising ethanol.