CN103772143A - Method for preparing industrial ethanol from acetic acid - Google Patents

Method for preparing industrial ethanol from acetic acid Download PDF

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Publication number
CN103772143A
CN103772143A CN201410008701.XA CN201410008701A CN103772143A CN 103772143 A CN103772143 A CN 103772143A CN 201410008701 A CN201410008701 A CN 201410008701A CN 103772143 A CN103772143 A CN 103772143A
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acetic acid
ethanol
no3
solution
cu
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CN201410008701.XA
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王立卓
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上海海源化工科技有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention relates to a method for preparing ethanol, and particularly relates to a method for preparing ethanol from acetic acid. The method adopts raw materials and a catalyst, wherein the raw materials are acetic acid and hydrogen. The method is characterized in that the catalyst is a Cu-based catalyst, and the method comprises the steps of loading the Cu-based catalyst into a reactor, and reducing with hydrogen at 220-270 DEG C; feeding the hydrogen and acetic acid at a molar ratio of (10-50):1 to enable contact between the raw materials and the catalyst; reacting for 24 hours at a reaction temperature of 180-300 DEG C under a reaction pressure of 0.5-6.0MPa; reacting to generate ethanol and water when the mass air speed of the acetic acid is 0.1-0.5/h; separating the product to obtain an ethanol product. The adopted Cu-based catalyst effectively adjusts the acid-base property of the catalyst, can inhibit the generation of diethyl ether, and converts acetic acid into ethanol to the greatest degree, thus the selectivity and stability are good, and the per-pass conversion of the reaction is high; meanwhile, the reaction conditions are mild, the energy consumption is low, and a good technical effect is obtained.

Description

—种由醋酸制备工业乙醇的方法 - acetic acid by the method of industrial preparation of ethanol

[技术领域] [Technical Field]

[0001] 本发明涉及一种制备乙醇的方法,具体的说是一种由醋酸制备工业乙醇的方法。 [0001] The present invention relates to a process for producing ethanol, specifically it is a method of industrial preparation of ethanol from acetic acid.

[背景技术] [Background technique]

[0002] 乙醇广泛应用于食品、医药、化工、燃料、国防等行业,作为一种十分重要的清洁燃料和汽油防爆剂组分,可大幅度降低燃烧的污染物排放。 [0002] Ethanol is widely used in food, medicine, chemicals, fuels, defense and other industries as a very important proof of clean fuel and gasoline component, can significantly reduce combustion emissions. 据全球可再生燃料联盟和F.0.Licht联合发布了全球乙醇产量年度预测报告,2011年全球乙醇产量约887亿升(2010年为858亿升),增幅超过3%,60%的乙醇用于汽车燃料。 According to the Global Renewable Fuels Alliance and F.0.Licht jointly issued its annual forecast of global ethanol production, global ethanol production in 2011 of about 88.7 billion liters (85.8 billion liters in 2010), an increase of more than 3%, 60% ethanol automotive fuel. 美国是目前燃料乙醇生产的第一大国,2006年美国乙醇产量为194.72亿升,2007年乙醇产能达到253.88亿升/年,另有308.47亿升/年的产能在建,总产能达到562.35亿升/年。 United States is the superpower of fuel ethanol production in 2006, US ethanol production was 19.472 billion liters in 2007, ethanol production capacity reached 25.388 billion liters / year, while 30.847 billion liters / year capacity under construction, total capacity reached 56.235 billion liters /year. 巴西由于其得天独厚的原料(甘蔗)优势,产量仅次于美国,生产工艺最无争议,成为全球最大的燃料乙醇出口国,产能也快速增长。 Brazil due to its unique raw material (sugarcane) advantages, production after the United States, the production process of the most non-controversial, the world's largest exporter of fuel ethanol production capacity is also growing rapidly.

[0003] 传统的乙醇生产主要依靠粮食发酵,成本高、效率低,由于影响全球的粮食平衡,遭到多数国家反对。 [0003] The traditional ethanol production is mainly dependent on food fermentation, high cost, low efficiency, due to the impact of the global food balance, most countries were opposed. 采用生物质(纤维素)发酵制乙醇,原料丰富、价廉,但集输和产品分离成本较高,且技术尚有待进一步完善成熟。 Use of biomass (cellulose) in ethanol fermentation, abundant raw materials, inexpensive, but high cost of product separation and gathering, and mature technology remains to be further improved. 目前煤制乙醇的工艺路线主要分为3种:一是合成气直接制乙醇;二是合成气生物法制乙醇,即以合成气(包括含一氧化碳和氢气的废气)经微生物发酵生产乙醇;三是合成气经醋酸加氢制乙醇。 Currently coal routing ethanol divided into three kinds: First, direct synthesis gas to ethanol; two biological preparation and ethanol synthesis gas, i.e. synthesis gas (an exhaust gas comprising carbon monoxide and hydrogen) to produce ethanol by microbial fermentation; Third syngas ethanol hydrogenation of acetic acid. 合成气生物法制乙醇,由于发酵需要停留长,难以连续化生产,成本较高;合成气直接制乙醇,转化率和选择性低,产品为混合物,需要提纯,技术仍处于研发阶段。 Biological synthesis gas SYSTEM ethanol fermentation due to the need to stay a long, continuous production is difficult and costly; direct synthesis gas to ethanol, low conversion rate and selectivity, the product mixture, purification need, technology still under development. 因此,在煤制乙醇的路线中,合成气经醋酸加氢制乙醇的技术路线由于选择性高,成本相对较低,易于大型化合规模化,具有良好的发展前景。 Thus, in the course of coal ethanol, acetic technical route syngas due to selective hydrogenation to ethanol is high, relatively low cost, easy to compound a large scale, has good prospects for development.

[0004] 2011年I月Celanese公司公开了利用钼/锡催化剂从醋酸选择性加氢生产乙醇的TCXTM专利技术。 [0004] Celanese Corporation, February 2011 I TCXTM patent discloses the use of a molybdenum / tin catalyst selective hydrogenation to produce ethanol from acetic acid. 该公司表示,采用TCXTM工艺生产乙醇的成本相当于以60美元/桶的原油生产汽油的成本,计划在美国德克萨斯的Clear Lake建设一套4万吨/年的天然气制乙醇装置,预计2012年底投产;主要用于生产燃料乙醇。 The company said the cost of using TCXTM process to produce ethanol is equivalent to a cost of $ 60 / barrel of crude oil to produce gasoline, planned in Clear Lake, Texas, USA Construction of a 40,000 tons / year of natural gas to ethanol plant, expected to by the end of 2012 and put into production; mainly used for the production of fuel ethanol.

[0005] 我国是全球第二大的汽油生产和消费国,2011年我国汽油的产量达8141.1万吨,表观消费量达7738.0万吨,预计2020年汽油消费量将达到1.2亿吨,柴油需求量为2.33亿吨。 [0005] Our country is world's second largest producer and consumer of gasoline, in 2011 China's output of gasoline amounted to 81.411 million tons, apparent consumption amounted to 77.38 million tons, is expected in 2020 gasoline consumption will reach 120 million tons, diesel demand the amount of 2.33 million tons. 我国能源结构的特点是:富煤、贫油、少气,我国煤炭资源总量为5.6万亿吨,其中已探明储量为I万亿吨,占世界总储量的11%,而石油、天然气仅占全球份额分别为2.4%、1.2%。 The characteristics of China's energy structure is: rich in coal, oil-poor, less gas, total coal resources in China is 5.6 trillion tons, which has proven reserves of I one trillion tons, accounting for 11% of the world's total reserves, while oil and gas only global share of respectively 2.4% and 1.2%. 2010年中国一次能源生产构成:原煤77.4%,原油9.7%,天然气4.3%,一次电力8.6%。 2010 China's primary energy production constituted: coal 77.4%, 9.7% crude oil, natural gas 4.3%, a 8.6% electricity. 在高油价时代,燃料替代是保障国家能源安全和降低成本有效途径之一。 In the era of high oil prices, fuel substitution is to protect national energy security and reduce the cost effective way. 研究表明,使用ElO车用乙醇汽油(乙醇10%),辛烷值可提高3%,可减排C025~30%,减排C02约10%。 Studies have shown that the use of ethanol gasoline ElO (10% ethanol), 3% increase in octane, can reduce emissions C025 ~ 30%, C02 about 10% reduction. 因此,发展乙醇汽油对改善环境、实现可持续发展具有重要意义。 Therefore, the development of ethanol gasoline has an important role in improving the environment and achieve sustainable development.

[0006] 目前我国每年消费约300万吨乙醇,并正在以年均8%~10%的速度快速增长。 [0006] At present, China's annual consumption of about 300 tonnes of ethanol, and is growing at an average annual rate of 8% to 10%. 2002年6月到2003年6月开展并完成了燃料乙醇的试点,2004年2月,国家发改委等八部门联合颁布了《车用乙醇汽油扩大试点方案》和《车用乙醇汽油扩大试点工作实施细则》,把推广使用乙醇汽油作为国家的一项战略性举措。 June 2002 to June 2003 carried out and completed the pilot fuel ethanol, in February 2004, the National Development and Reform Commission and other eight departments jointly issued the "vehicle to expand ethanol gasoline pilot program" and "the car to expand the pilot ethanol gasoline implementation Rules, "to promote the use of ethanol gasoline as a strategic move countries. 目前我国生物燃料乙醇技术已成熟,黑龙江、吉林、辽宁、河南、安徽5省及湖北、河北、山东、江苏部分地区已基本实现车用乙醇汽油替代普通无铅汽油。 At present, China Bio-ethanol technology has matured, Heilongjiang, Jilin, Liaoning, Henan, Anhui provinces and 5 parts of Hubei, Hebei, Shandong, Jiangsu has basically replace regular unleaded gasoline car gasoline with ethanol. 国内95%以上的乙醇采用粮食发酵法生产,随着燃料乙醇产业的发展和需求量的不断增长,致使粮食供应日渐紧张,价格急涨,生产成本上升。 More than 95% of the domestic ethanol production using food fermentation, with the continuous development and growth in demand for fuel ethanol industry, resulting in increasingly tight food supply, soaring prices, rising production costs. 未来燃料乙醇的发展应“不与人争粮,不与粮争地”。 Future development of fuel ethanol should "not competing with food, not with the food fight."

[0007] 现在我规定可在汽油中添加10%的乙醇,若按此比例计算,推广至全国范围,我国燃料乙醇需求量约为6.6X 106t/a (按我国汽油需求为6.6 X 107t/a计)。 [0007] provisions now I can add 10% ethanol in gasoline, if this ratio calculation, extended to the country, China's demand for fuel ethanol is about 6.6X 106t / a (according to our gasoline demand is 6.6 X 107t / a meter). 而目前我国主要的5家燃料乙醇生产企业总生产能力才1.42X 106t/a(见表1),因此燃料乙醇的市场潜力巨大。 At present, China's five major fuel ethanol producers a total production capacity of only 1.42X 106t / a (see Table 1), and therefore huge market potential for fuel ethanol.

[0008] 表1我国主要燃料乙醇生产企业情况(万吨/年) [0008] Table 1 China's major fuel ethanol producers case (tons / year)

Figure CN103772143AD00041

[0010] 乙醇的生产方法主要有发酵法和化学法。 [0010] Production of ethanol fermentation are mainly and chemical methods. 发酵法的主要原料是农作物,通过利用农作物中的淀粉发酵获得乙醇。 The main raw material is the fermentation of crops, using a starch obtained by ethanol fermentation of crops. 化学法主要是以乙烯为原料,通过乙烯水合生产乙醇。 Chemical mainly ethylene as raw material, the production of ethanol by hydration of ethylene. 我国乙醇的生产主要以发酵法为主,占乙醇总量的96.5%。 The main production of ethanol fermentation method, accounting for 96.5% of total ethanol. 从表1的统计可以看出,我国发酵法生产乙醇主要原料集中在玉米和小麦。 Statistics can be seen from Table 1, the production of ethanol by fermentation mainly concentrated in the raw material corn and wheat. 与燃料乙醇第一生产大国美国相比。 Compared with the first fuel ethanol-producing countries the United States. 我国燃料乙醇生产成本较高,每吨乙醇需消耗3.3吨玉米和1.5吨煤,乙醇的生产成本在8000元以上。 Higher production costs of fuel ethanol, 3.3 tons per ton of corn required to consume ethanol and 1.5 tons of coal, the production cost of ethanol is more than 8,000 yuan.

[0011] 随着国民经济的持续快速增长,未来乙醇的需求量将大幅提高,若乙醇汽油在国内全面推广应用,预计2015年全国燃料乙醇的需求量将超过1000万吨,因此发展低成本的乙醇合成新技术是当务之急。 [0011] With the continued rapid growth of the national economy, the future will be a substantial increase in the demand for ethanol, ethanol gasoline in the country if a comprehensive application, expected demand for fuel ethanol by 2015 the country will be over 10 million tons, so the development cost ethanol synthesis technology is a priority. 国内目前尚处于实验室或中试阶段。 China is still in the laboratory or pilot stage.

[0012] 与此同时,伴随着纤维、涂料、黏合剂行业的发展,我国醋酸行业产能快速扩张,2010年我国累计生产冰醋酸383.80万吨,同比增长29.29%,醋酸生产明显供大于求,企业经济效益大幅下降。 [0012] At the same time, with the development of fibers, coatings, adhesives industry, China's acetic acid industry, the rapid expansion of production capacity in 2010, China's total production of acetic acid 3.838 million tons, an increase of 29.29%, the production of acetic acid obvious oversupply, companies sharp economic decline. 2011年全国聚乙烯醇产能达到87.7万吨,副产醋酸甲酯约145万吨,由于醋酸甲酯市场容量很有限,目前大多数企业只能通过水解、分离回收醋酸及甲醇循环使用,回收装置工艺流程复杂,投资高,能耗高,少数厂家直接销售粗醋酸甲酯。 2011 national production capacity of 877,000 tons of polyvinyl alcohol, methyl acetate byproduct about 145 million due to methyl acetate market capacity is very limited, most companies can only by hydrolysis, separation and recovery of acetic acid and methanol, recycling, recovery complex process, high investment, high energy consumption, direct sales few manufacturers crude methyl acetate. 因此发展醋酸/醋酸甲酯加氢制乙醇技术不仅具有原料和市场优势,而且可促进相关行业的效益提升。 Therefore, the development of acetate / acetic acid methyl ester hydrogenation of ethanol technology not only has the advantages of raw materials and markets, but also promote the benefits related industries upgrade.

[0013] 因此,醋酸/醋酸酯加氢制乙醇工艺具有技术经济上的可行性。 [0013] Thus, the hydrogenation process of ethanol acetate / acetate having a technical and economic feasibility. 开发醋酸/醋酸酯加氢制备乙醇技术,形成符合我国特色的自主知识产权的煤基乙醇大型化成套技术,对于提升醋酸和聚乙烯醇行业的经济效益,大规模生产替代燃料,保障国家能源安全,具有重大战略意义和良好发展前景。 Large-scale coal-based ethanol Complete Technology Development acetate / acetic ester hydrogenation of ethanol technology, independent intellectual property rights in line with Chinese characteristics, and to enhance the economic efficiency of acetic acid and polyvinyl alcohol industry, large-scale production of alternative fuels, ensure national energy security It is of great strategic significance and good development prospects.

[0014] 据英国泰可荣全球化学公司统计,2012年,我国醋酸的有效产能是752万吨,而醋酸需求量仅为400万吨左右。 [0014] According to the British Thai glorious and global chemical company statistics, in 2012, the effective capacity of acetic acid is 7.52 million tons, while the demand for acetic acid is only 400 million tons. 河南义马气化厂,重庆扬子江乙酰化工有限公司,安徽定远盐化工,宁夏英力特宁东煤基化学有限公司,内蒙乌海煤业等都将于近期投产新的醋酸项目。 Henan Yima Gasification Plant, Chongqing Yangtze Acetyl Chemicals Co., Ltd., Anhui Dingyuan salt chemical industry, coal-based Ningxia Yinglite tnine East Chemical Co., Ltd., Meng Wuhai Coal and so will soon put into operation a new acetic acid project. 虽然醋酸乙烯、醋酸酯、PTA产能的规模将继续稳步增长,但在严重过剩的醋酸产能前体下,也无力将醋酸消耗,通过醋酸加氢制备乙醇如果能够大型化,将有利于缓解目前醋酸的进一步利用问题,为实现乙醇制备提供一条可行的途径。 Although vinyl acetate, acetate, scale PTA production capacity will continue to grow steadily, but in severe excess acetic acid production capacity precursors, but also unable to acetic acid consumed by acetic acid hydrogenation to ethanol if able size, will help to ease the current acetate the further utilization, provides a feasible way for the realization of ethanol.

[0015] US4517391专利中,采用Co催化剂用于醋酸加氢反应。 [0015] US4517391 patent, the use of Co catalysts for the hydrogenation of acetic acid. 催化剂中Co含量不低于50%,入口温度在230~270°C,反应压力27MPa条件下,生成乙醇收率达97%。 Catalyst Co content is not less than 50%, the inlet temperature at 230 ~ 270 ° C, the reaction pressure 27MPa conditions, the formation of ethanol 97% yield. 该反应压力比较苛刻,工业化生成较难。 The reaction pressure is relatively harsh, more difficult to generate industrialization.

[0016] US2607807专利使用Ru基为催化剂,结果发现,在70MPa条件下进行醋酸加氢,乙醇收率可以达到88%,降低反应压力至20MPa,乙醇最大收率41%。 [0016] US2607807 patent Ru-based catalyst, and found that, acetic acid was hydrogenated under conditions 70MPa, the ethanol yield of 88% can be achieved, reducing the reaction pressure to 20 MPa or, the maximum yield of 41% ethanol.

[0017] US7608744B1专利采用Pt系列催化剂,催化剂组成中Pt含量为l%,Co含量为10%时,在反应温度250°C,氢气压力22bar,醋酸转化率达38%,生成乙醇选择性达96%,Pt系列催化剂成本昂贵。 When [0017] US7608744B1 patent using Pt catalysts, the catalyst composition amount of Pt l%, Co content was 10% at a reaction temperature of 250 ° C, a hydrogen pressure of 22 bar, the conversion rate of 38% acetic acid, the formation of ethanol selectivity of 96 %, Pt catalysts are expensive.

[0018] 综上可以发现,现有技术应用于醋酸加氢制备乙醇的过程中,存在应条件苛刻、单程转化率低导致能耗高的问题,且催化剂成本高昂。 [0018] can be found in summary, the prior art hydrogenation of acetic acid applied to the process of ethanol, there should be harsh conditions, result in high per pass conversion of low energy consumption, high cost and the catalyst.

[发明内容] [SUMMARY]

[0019] 本发明所要解决的技术问题是现有醋酸加氢催化剂在制备乙醇过程中反应条件苛刻、单程转化率低导致能耗高的问题,和催化剂成本高昂的问题,本发明提供一种新的制备乙醇的方法。 [0019] The present invention solves the prior art problem acetate hydrogenation catalyst in the harsh reaction conditions during the production of ethanol, resulting in a low per pass conversion of high energy consumption, and the problem of high catalyst cost, the present invention provides a new the method of producing ethanol. 该方法具有催化剂反应条件温和、催化剂活性高、成本低的优点。 This method has a catalyst mild reaction conditions, high catalyst activity and low cost.

[0020] 为解决上述技术问题,本发明采用技术方案如下:包括原料及催化剂,原料为醋酸和氢气,其特征在于催化剂采用Cu基催化剂,所述Cu基催化剂以重量百分比计由以下组分构成:15.0~40.0%Cu或其氧化物,10.0~25.0%Ζη或其氧化物,1.0~10.0%Μη或其氧化物,1.0 ~15.0%A1203, 15.0 ~40%Si02,0.5 ~5.0% 选自Co、Ce、La、Mg、Ba 或其氧化物中的至少一种;将Cu基催化剂装填于反应器中,经220~270°C氢气还原后,将氢气与醋酸以摩尔比10~50:1进料,原料与催化剂接触,在反应温度为180~300°C,反应压力为0.5~6.0MPa,反应时间24h,醋酸质量空速为0.1~0.5h-1的条件下,反应生成乙醇和水,通过产物分离得到乙醇产品。 [0020] To solve the above problems, the present invention adopts the following technical solution: for raw materials and a catalyst, the raw material for the hydrogen and acetic acid, wherein the catalyst is a Cu based catalyst, the Cu-based catalyst, in weight percent consists of the following components : 15.0 ~ 40.0% Cu or an oxide, 10.0 ~ 25.0% Ζη or an oxide thereof, 1.0 ~ 10.0% Μη or an oxide thereof, 1.0 ~ 15.0% A1203, 15.0 ~ 40% Si02,0.5 ~ 5.0% selected from Co , Ce, La, Mg, Ba, or an oxide of at least one; Cu based catalyst loaded in the reactor, by 220 ~ 270 ° C after reduction with hydrogen, hydrogen gas and acetic acid in a molar ratio of 10 to 50: 1 feed, feedstock is contacted with the catalyst at a reaction temperature of 180 ~ 300 ° C, the reaction pressure 0.5 ~ 6.0MPa, reaction time 24h, acetic acid under the conditions of weight hourly space velocity of 0.1 ~ 0.5h-1, the reaction of ethanol and water , the product obtained by separating the ethanol product.

[0021] 上述技术方案中: [0021] The technical solution:

[0022] 原料中醋酸以纯醋酸或醋酸溶液的形式进料,醋酸的浓度以重量百分比计为50 ~100%,进料量为0.2 ~0.6ml/min,氢气流量3500 ~5000ml/min。 [0022] The feedstock in the form of pure acetic acid or acetic acid in the acetic acid feed solution, the concentration of acetic acid in weight percent of 50 to 100%, the feed amount of 0.2 ~ 0.6ml / min, hydrogen flow rate of 3500 ~ 5000ml / min.

[0023] 工艺参数上,醋酸的质量空速优选范围为0.1-OjtT1 ;氢气/醋酸的摩尔比优选范围为20~40:1 ;所述加氢反应温度优选范围为220~260°C;反应压力优选范围为1.0~ [0023] the process parameters, WHSV is preferably in the range of acetic acid 0.1-OjtT1; molar ratio of hydrogen / acetic acid is preferably in the range of 20 to 40: 1; the hydroprocessing reaction temperature is preferably in the range of 220 ~ 260 ° C; Reaction The pressure is preferably in the range of 1.0 ~

4.0MPa ; 4.0MPa;

[0024] 催化剂以重量百分比计:Cu或其氧化物用量优选范围为15.0~35.0% ;Zn或其氧化物用量的优选范围为15.0~20.0% ;A1203用量优选范围为5.0~15.0% ;Si02用量优选范围为15.0~30.0%;选自Co、Ce、La、Mg、Ba或其氧化物中的至少一种用量优选范围为 [0024] The catalyst in weight percent: Cu is preferably used in an amount or a range of 15.0 to 35.0% of an oxide; Zn, or an oxide is preferably used in an amount range of 15.0 ~ 20.0%; A1203 is preferably used in an amount in the range of 5.0 ~ 15.0%; Si02 dosage preferably in the range of 15.0 to 30.0%; is selected from Co, Ce, La, Mg, Ba, or an amount of at least one oxide is preferably in the range of

1.0 ~5.0%。 1.0% to 5.0%.

[0025] 制备催化剂包括以下步骤:将40%硅溶胶和15%铝溶胶于1.0-1.2L中水中加热至70-85°C形成溶液I,或称取一定量Al2O3加入到1.0L中水中加热至80°C形成溶液I ;将所需量的选自含(:11、211、(:0、06、1^、1%、8&、41和Mn可溶性物溶于1.0L水中,在75_80°C油浴中加热搅拌形成溶液2 ;以1.0mol/L碳酸钠水溶液或1.0mol/L碳酸钾水溶液或氨水为溶液3 ;溶液2和溶液3同时滴入溶液I中并控制pH值6.5-10得到沉淀物,滴加完全后经过滤、洗涤、干燥、焙烧、成型后得到Cu基催化剂。 Preparation [0025] The catalyst comprising the steps of: 40% silica and 15% alumina sol was heated in 70-85 ° C water 1.0-1.2L to form a solution I, or a weighed amount of Al2O3 added to the heated water in 1.0L 80 ° C to form a solution I; containing a desired amount of selected (: 11, 211, (: 0,06,1 ^, 1%, & 8, and 41 was dissolved in 1.0L of water soluble Mn, at 75_80 ° C oil bath and heated with stirring to form a solution 2; at 1.0mol / L sodium carbonate aqueous solution or 1.0mol / L aqueous potassium carbonate or aqueous ammonia solution is 3; and the solution 2 solution 3 solution was added dropwise while controlling the pH value of the I and 6.5-10 the precipitate obtained was added dropwise after completion was filtered, washed, dried, calcined, obtained after forming Cu based catalyst.

[0026] 由于在醋酸加氢生成乙醇的过程中,可能发生多种副反应,如:醋酸不完全加氢生成乙醛,直接加氢生成的乙醇与醋酸通过酯化生成醋酸乙酯,乙醇进一步脱水生成乙烯,乙烯进一步加氢生成乙烷,还可能通过耦合生成仲丁醇等。 [0026] Since during the hydrogenation of acetic acid in ethanol, a variety of side effects may occur, such as: incomplete hydrogenation of acetic acid to acetaldehyde, ethanol and the direct hydrogenation of ethyl acetate by esterification of acetic acid generated, further ethanol dehydration, ethylene oxide is further hydrogenation, and the like may also be generated by coupling butanol. 因此,设计合适的催化剂采用适宜的工艺条件是实现醋酸选择加氢制备乙醇的关键。 Therefore, the design of suitable process conditions using a suitable catalyst is key to achieving the selective hydrogenation of acetic acid to ethanol. 采用Pt基催化剂时,反应转化率低。 When using Pt-based catalyst, the reaction conversion rate is low. 而本发明涉及的Cu基催化剂,通过引入CoO、CeO2、MgO、CaO、BaO等氧化物至少其中的一种对催化剂进行修饰,有效调节催化剂的酸碱性,能够抑制乙醚的生成,最大程度的将乙酸转化为乙醇,通过调变催化剂酸中心的数量与酸强度通过氧化物的种类,从而使制备的Cu基催化剂具有良好的选择性和稳定性。 The present invention relates to a Cu-based catalyst, wherein one of the catalyst by introducing CoO, CeO2, MgO, CaO, BaO modified oxides such as at least effectively regulate the pH of the catalyst, can suppress generation of diethyl ether, the maximum degree of the acid is converted to ethanol by intensity modulation with an acid number of acid centers of the catalyst species through the oxide so that Cu-based catalysts prepared with good selectivity and stability.

[0027] 使用本发明提供的方法,在入口反应温度245°C、反应压力3.0MPa,原料质量空速为0.3h_1,氢气与醋酸的摩尔比为25.0:1的反应条件下应用于醋酸选择加氢制备乙醇,当醋酸转化率为92%时,生成乙醇的选择性达96.5%,反应单程转化率高,同时反应条件温和,能耗低,取得了良好的技术效果。 [0027] The present invention provides the use, in the inlet reaction temperature of 245 ° C, reaction pressure 3.0MPa, WHSV of feed 0.3h_1, the molar ratio of hydrogen to acetic acid was 25.0: selecting the reaction conditions applied acetate plus 1 hydrogen ethanol, acetic acid when the conversion was 92%, the formation of ethanol selectivity of 96.5%, per pass conversion rate of the reaction, while the reaction conditions are mild, low energy consumption, good technical effect achieved.

[具体实施方式] [Detailed ways]

[0028] 下面通过实施例对本发明作进一步阐述。 [0028] The following examples further illustrated the invention.

[0029] 实施例1 [0029] Example 1

[0030] 按照比例称取60.0g40%硅溶胶于1.0L中水中加热至80°C形成溶液I ;称取121.5gCu (NO3)2.3Η20、73.5g Zn (NO3) 2.6Η20、10.6g La (NO3) 3.6Η20、5.Ig Ba (NO3)2,36.8gAl(NO3)3.9H20、重量百分比为50%Mn(NO3)2溶液8.2g—并溶于1.0L水中,在80°C油浴中加热搅拌形成溶液2。 [0030] Weigh scale 1.0L 60.0g40% silica sol in water and heated to 80 ° C to form a solution I; weighed 121.5gCu (NO3) 2.3Η20,73.5g Zn (NO3) 2.6Η20,10.6g La (NO3 ) 3.6Η20,5.Ig Ba (NO3) 2,36.8gAl (NO3) 3.9H20, the weight percentage of 50% Mn (NO3) 2 was dissolved in 1.0L 8.2g- and water and heated in an oil bath at 80 ° C 2 was stirred to form a solution. 称取106.0g无水碳酸钠于烧杯中,加入蒸馏水至1L,搅拌溶解配成 106.0g of anhydrous sodium carbonate was weighed in a beaker, distilled water was added to 1L, stirring to dissolve dubbed

1.0mol/L碳酸钠水溶液为溶液3。 1.0mol / L sodium carbonate aqueous solution is 3. 溶液2和溶液3同时滴加往溶液I中,保持pH为7.0左右得到沉淀物,过滤得到沉淀物。 2 and 3 while the solution was added dropwise to the solution I, to keep the pH of about 7.0 to give a precipitate was filtered to give a precipitate. 沉淀物经干燥、焙烧成型得到催化剂I (以重量百分比计为:40%Cu0-20%Zn0%-4%Lal203-5%Al203-3%Ba0-4%Mn02-24%Si02) The precipitate was dried to obtain a calcined molded catalyst I (in percent by weight: 40% Cu0-20% Zn0% -4% Lal203-5% Al203-3% Ba0-4% Mn02-24% Si02)

[0031] 装填该催化剂50g于反应器中,经过250°C氢气还原后,以纯醋酸为原料保持进料量为0.4ml/min,氢气流量3500ml/min,反应温度控制在240°C,反应压力1.5MPa,反应24h后,醋酸转化率91.5%,生成乙醇选择性94.5%。 After [0031] 50g of the catalyst packed in the reactor, 250 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.4ml / min, hydrogen flow rate of 3500ml / min, the reaction temperature is controlled at 240 ° C, the reaction pressure 1.5MPa, reaction 24h, acetic acid 91.5% conversion, 94.5% selectivity to ethanol.

[0032] 实施例2 [0032] Example 2

[0033] 按照比例称取78.0g40%硅溶胶和46.7gl5%铝溶胶于1.0L中水中加热至80 °C 形成溶液I ;称取一定量91.13g Cu (NO3) 2.3H20、73.50g Zn (NO3) 2.6Η20、19.4gCo (NO3)2.6Η20、8.54gBa(N03)2、重量百分比为50%Mn (NO3) 2 溶液14.4g—并溶于1.0L 水中,在80°C油浴中加热搅拌形成溶液2。 [0033] Weigh scale 78.0g40% 46.7gl5% silica sol and alumina sol in 1.0L of water was heated at 80 ° C to form a solution I; amount weighed 91.13g Cu (NO3) 2.3H20,73.50g Zn (NO3 ) 2.6Η20,19.4gCo (NO3) 2.6Η20,8.54gBa (N03) 2, the weight percentage of 50% Mn (NO3) 2 was dissolved in 1.0L of water and 14.4g-, heated at 80 ° C with stirring in an oil bath formed solution 2. 称取106g无水碳酸钠于烧杯中,加入蒸馏水至1L,搅拌溶解配成1.0mol/L碳酸钠水溶液为溶液3。 106g of anhydrous sodium carbonate was weighed in a beaker, distilled water was added to 1L, stirred to dissolve dubbed 1.0mol / L sodium carbonate aqueous solution is 3. 溶液2和溶液3同时滴加至溶液I中,保持pH为7.5左右得到沉淀物,过滤得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, to keep the pH of about 7.5 to give a precipitate was filtered to give a precipitate. 沉淀物经干燥、焙烧成型得到催化剂2 (以重量百分比计为:30%Cu0-20%Zn0%-5%Co0-7%Al203-5%Ba0-7%Mn02-31%Si02) The precipitate was dried, calcined catalyst obtained by molding 2 (in percent by weight: 30% Cu0-20% Zn0% -5% Co0-7% Al203-5% Ba0-7% Mn02-31% Si02)

[0034] 装填该催化剂50g于反应器中,经过250°C氢气还原后,以纯醋酸为原料保持进料量为0.4ml/min,氢气流量4000ml/min,反应温度控制在250°C,反应压力2.5MPa,反应24h后,醋酸转化率92.5%,生成乙醇选择性95.2%。 After [0034] 50g of the catalyst packed in the reactor, 250 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.4ml / min, hydrogen flow rate of 4000ml / min, the reaction temperature is controlled at 250 ° C, the reaction pressure 2.5MPa, reaction 24h, acetic acid 92.5% conversion, 95.2% selectivity to ethanol.

[0035] 实施例3 [0035] Example 3

[0036] 按照比例称取100g40%硅溶胶和100gl5%铝溶胶于1.3L中水中加热至75°C形成溶液I ;称取75.94g Cu(NO3)2.3H20、91.84g Zn (NO3) 2.6H20、19.4g Co (NO3) 2.6H20、 [0036] Weigh scale 100g40% 100gl5% silica sol and alumina sol in 1.3L of water was heated at 75 ° C to form a solution I; weighed 75.94g Cu (NO3) 2.3H20,91.84g Zn (NO3) 2.6H20, 19.4g Co (NO3) 2.6H20,

2.52gCe (NO3)2.6H20、Ba(NO3)2、重量百分比为50%Mn (NO3)2 溶液14.4g 溶于1.0L 水中,在75°C油浴中加热搅拌形成溶液2。 2.52gCe (NO3) 2.6H20, Ba (NO3) 2, the weight percentage of 50% Mn (NO3) 2 was dissolved in 14.4g 1.0L of water was heated at 75 ° C in an oil bath with stirring to form a solution 2. 称取106g无水碳酸钠于烧杯中,加入蒸馏水至1L,搅拌溶解配成l.0mol/L碳酸钠水溶液为溶液3。 106g of anhydrous sodium carbonate was weighed in a beaker, distilled water was added to 1L, stirred to dissolve dubbed l.0mol / L aqueous sodium carbonate solution is 3. 溶液2和溶液3同时滴加至溶液I中,保持pH为6.5左右得到沉淀物,过滤得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, to keep the pH is about 6.5 to give a precipitate was filtered to give a precipitate. 沉淀物干燥、焙烧成型得到催化剂3 (以重量百分比计为:25%Cu0-25%Zn0%-5%Co0-l%Ce02-15%Al203-5%Ba0-7%Mn02-17%Si02) The precipitate was dried to obtain a calcined shaped catalyst 3 (in percent by weight: 25% Cu0-25% Zn0% -5% Co0-l% Ce02-15% Al203-5% Ba0-7% Mn02-17% Si02)

[0037] 装填该催化剂50g于反应器中,经过230°C氢气还原后,以纯醋酸为原料保持进料量为0.4ml/min,氢气流量4500ml/min,反应温度控制在250°C,反应压力3.0MPa,反应24h后,醋酸转化率93.5%,生成乙醇选择性95.3%。 [0037] 50g of the catalyst packed in the reactor, 230 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.4ml / min, hydrogen flow rate of 4500ml / min, the reaction temperature is controlled at 250 ° C, the reaction pressure 3.0MPa, reaction 24h, acetic acid conversion rate was 93.5%, the selectivity to ethanol was 95.3%.

[0038] 实施例4 [0038] Example 4

[0039] 按照比例称取162.5g40%硅溶胶和134.0gl5%铝溶胶于1.2L中水中加热至85°C形成溶液I ;称取182.3g Cu (NO3)2.3Η20、147.0gZn(NO3)2.6Η20、64.Ig Mg(NO3)2.6Η20、38.8gCo (NO3)2.6Η20、17.Ig Ba(NO3)2、重量百分比为50%Mn (NO3)2 溶液16.5g—并溶于1.0L水中,在80°C油浴中加热搅拌形成溶液2。 [0039] Weigh scale 162.5g40% 134.0gl5% silica sol and alumina sol in 1.2L of water was heated at 85 ° C to form a solution I; weighed 182.3g Cu (NO3) 2.3Η20,147.0gZn (NO3) 2.6Η20 , 64.Ig Mg (NO3) 2.6Η20,38.8gCo (NO3) 2.6Η20,17.Ig Ba (NO3) 2, the weight percentage of 50% Mn (NO3) 2 was dissolved in 1.0L of water and 16.5g-, in 80 ° C oil bath and heated with stirring to form a solution 2. 以氨水为溶液3。 3 in a solution of ammonia. 溶液2和溶液3同时滴加至溶液I中,保持PH为10左右得到沉淀物,95°C蒸发掉溶剂得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, PH is maintained about 10 to give a precipitate, 95 ° C the solvent was evaporated to give a precipitate. 沉淀物经洗涤、干燥、焙烧成型得到催化剂4 (以重量百分比计为:30%Cu0-20%Zn0%-5%Co0-5%Mg0-10%Al203-5%Ba0-2%Mn02-13%Si02) The precipitate was washed, dried, calcined catalyst obtained by molding 4 (in weight percent of: 30% Cu0-20% Zn0% -5% Co0-5% Mg0-10% Al203-5% Ba0-2% Mn02-13% si02)

[0040] 装填该催化剂50g于反应器中,经过240°C氢气还原后,以纯醋酸为原料保持进料量为0.4ml/min,氢气流量4000ml/min,反应温度控制在250°C,反应压力4.0Mpa,反应24h后,醋酸转化率90.5%,生成乙醇选择性94.8%。 [0040] 50g of the catalyst packed in the reactor, 240 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.4ml / min, hydrogen flow rate of 4000ml / min, the reaction temperature is controlled at 250 ° C, the reaction pressure 4.0MPa, after 24h the reaction, the conversion rate was 90.5% acetate, 94.8% selectivity to ethanol.

[0041] 实施例5 [0041] Example 5

[0042] 按照比例称取54g Al2O3加入到1.0L中水中加热至80°C形成混合液I ;称取151.9gCu (NO3)2.3Η20、147.0g Zn (NO3) 2.6Η20、38.8g Co (NO3) 2.6Η20、35.3gCe (NO3)2.6H20重量百分比为50%Mn (NO3)2溶液57.6g 一并溶于1.0L水中,在80°C油浴中加热搅拌形成溶液2。 [0042] Weigh 54g Al2O3 scale was added to 1.0L of water and heated to 80 ° C the mixture formed in I; weighed 151.9gCu (NO3) 2.3Η20,147.0g Zn (NO3) 2.6Η20,38.8g Co (NO3) 2.6Η20,35.3gCe (NO3) 2.6H20 weight percentage of 50% Mn (NO3) 2 was dissolved in 1.0L of water was 57.6g together, heated at 80 ° C in an oil bath with stirring to form a solution 2. 配制1.0mol/L碳酸钠水溶液为溶液3。 Formulated 1.0mol / L sodium carbonate aqueous solution is 3. 溶液2和溶液3同时滴加至溶液I中,保持PH为7.5左右得到沉淀物,过滤得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, about 7.5 maintained PH resulting precipitate was filtered to give a precipitate. 沉淀物经过干燥,焙烧、成型得到催化剂5(以重量百分比计为25%Cu0-20%Zn0%-5%Co0-4%Ce02-7%Ce02-5%Ba0-7%Mn02-27%Al203) The precipitate was dried, calcined, obtained by molding the catalyst 5 (in weight percent of 25% Cu0-20% Zn0% -5% Co0-4% Ce02-7% Ce02-5% Ba0-7% Mn02-27% Al203)

[0043] 装填该催化剂40g于反应器中,经过220°C氢气还原后,以纯醋酸为原料保持进料量为0.4ml/min,氢气流量4000ml/min,反应温度控制在220°C,反应压力5.0Mpa,反应24h后,醋酸转化率90.5%,生成乙醇选择性93.8%。 [0043] 40g of the catalyst packed in the reactor, 220 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.4ml / min, hydrogen flow rate of 4000ml / min, the reaction temperature is controlled at 220 ° C, the reaction pressure of 5.0 MPa, after 24h the reaction, the conversion rate was 90.5% acetate, 93.8% selectivity to ethanol.

[0044] 实施例6 [0044] Example 6

[0045] 按照比例称取97.5g40%硅溶胶和15%铝溶胶70.0g于1.0L中水中加热至80°C形成溶液I ;称取136.7g Cu (NO3) 2.3Η20、110.2g Zn (NO3) 2.6Η20、29.Ig Co (NO3) 2.6Η20、 [0045] Weigh scale 97.5g40% 15% silica sol and 70.0g alumina sol was heated in 1.0L of water to 80 ° C to form a solution I; weighed 136.7g Cu (NO3) 2.3Η20,110.2g Zn (NO3) 2.6Η20,29.Ig Co (NO3) 2.6Η20,

5.1gBa (NO3) 2、重量百分比为50%Mn (NO3) 2溶液61.7g —并溶于1.0L水中,在80°C油浴中加热搅拌形成溶液2。 5.1gBa (NO3) 2, the weight percentage of 50% Mn (NO3) 2 solution 61.7g - and dissolved in 1.0L of water, was heated at 80 ° C in an oil bath with stirring to form a solution 2. 配制1.0mol/L碳酸钾水溶液为溶液3。 Formulated 1.0mol / L aqueous potassium carbonate solution is 3. 溶液2和溶液3同时滴加至溶液I中,保持PH为7.5左右得到沉淀物,过滤得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, about 7.5 maintained PH resulting precipitate was filtered to give a precipitate. 沉淀物经干燥、焙烧得到催化剂6 (以重量百分比计为30%Cu0-20%Zn0%-5%Co0-7%Al203-2%Ba0-10%Mn02-26%SiO2) The precipitate was dried and calcined catalyst to give 6 (weight percentage of 30% Cu0-20% Zn0% -5% Co0-7% Al203-2% Ba0-10% Mn02-26% SiO2)

[0046] 装填该催化剂40g于反应器中,经过250°C氢气还原后,以纯醋酸为原料保持进料量为0.2ml/min,氢气流量4000ml/min,反应温度控制在260°C,反应压力3.5Mpa,反应24h后,醋酸转化率95.2%,生成乙醇选择性93.2%。 [0046] 40g of the catalyst packed in the reactor, 250 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.2ml / min, hydrogen flow rate of 4000ml / min, the reaction temperature is controlled at 260 ° C, the reaction pressure 3.5MPa, reaction 24h, acetic acid conversion rate was 95.2 percent, with 93.2% selectivity to ethanol.

[0047] 实施例7 [0047] Example 7

[0048] 按照比例称取67.5g40%硅溶胶于1.2L中水中加热至85 °C形成溶液I ;称取91.1g Cu (NO3) 2.3Η20、73.5g Zn (NO3) 2.6Η20、32.IMg(NO3)2.6Η20、19.4g Co (NO3) 2.6H20、8.5gBa (NO3)2、重量百分比为50%Mn (NO3) 2溶液16.5g 一并溶于1.0L水中,在80°C油浴中加热搅拌形成溶液2。 [0048] Weigh scale 1.2L 67.5g40% silica sol in water and heated to 85 ° C to form a solution I; weighed 91.1g Cu (NO3) 2.3Η20,73.5g Zn (NO3) 2.6Η20,32.IMg ( NO3) 2.6Η20,19.4g Co (NO3) 2.6H20,8.5gBa (NO3) 2, the weight percentage of 50% Mn (NO3) 2 was dissolved in 1.0L of water was 16.5g together, heated at 80 ° C in an oil bath 2 was stirred to form a solution. 以氨水为溶液3。 3 in a solution of ammonia. 溶液2和溶液3同时滴加至溶液I中,保持pH为10左右得到沉淀物,加热至90°C蒸干得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, maintaining the pH of about 10 to give a precipitate, heated to 90 ° C and evaporated to dryness to give a precipitate. 沉淀物经过洗涤、焙烧、成型得到催化剂7(以重量百分比计为:30%Cu0-20%Zn0%-5%Co0-5%Mg0-5%Ba0-8%Mn02-27%SiO2) The precipitate after washing, calcining, the catalyst obtained by molding 7 (in percent by weight: 30% Cu0-20% Zn0% -5% Co0-5% Mg0-5% Ba0-8% Mn02-27% SiO2)

[0049] 装填该催化剂40g于反应器中,经过250°C氢气还原后,以纯醋酸为原料保持进料量为0.4ml/min,氢气流量4000ml/min,反应温度控制在260°C,反应压力2.0Mpa,反应24h后,醋酸转化率87.5%,生成乙醇选择性91.2%。 [0049] 40g of the catalyst packed in the reactor, 250 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.4ml / min, hydrogen flow rate of 4000ml / min, the reaction temperature is controlled at 260 ° C, the reaction pressure 2.0Mpa, the reaction after 24h, acetic acid conversion rate was 87.5 percent, with 91.2% selectivity to ethanol.

[0050] 实施例8 [0050] Example 8

[0051] 按照比例称取125.0g40%硅溶胶和15%铝溶胶200g于1.5L中水中加热至70V形成溶液I ;称取182.3g Cu (NO3) 2.3Η20、110.2g Zn (NO3) 2.6Η20、25.2g Ce (NO3) 2.6H20、17.1gBa(NO3)2,重量百分比为50%Mn (NO3)2溶液41.2g—并溶于1.0L水中,在70°C油浴中加热搅拌形成溶液2。 [0051] Weigh scale 125.0g40% silica and 15% alumina sol was heated to 70V 200g in 1.5L of water to form a solution I; weighed 182.3g Cu (NO3) 2.3Η20,110.2g Zn (NO3) 2.6Η20, 25.2g Ce (NO3) 2.6H20,17.1gBa (NO3) 2, the weight percentage of 50% Mn (NO3) 2 was dissolved in 1.0L of water and 41.2g-, heated at 70 ° C in an oil bath with stirring to form a solution 2. 配制1.5mol/L碳酸钠水溶液为溶液3。 Formulated 1.5mol / L sodium carbonate aqueous solution is 3. 溶液2和溶液3同时滴加至溶液I中,保持pH为8.0左右得到沉淀物,过滤得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, maintaining a pH of about 8.0 resulting precipitate was filtered to give a precipitate. 沉淀物经过干燥、焙烧,成型得到催化剂8 (以重量百分比计为30%Cu0-15%Zn0%-5%Ce02-15%Al203-5%Ba0-5%Mn02-25%SiO2) The precipitate was dried, calcined, obtained by molding the catalyst 8 (in percent by weight 30% Cu0-15% Zn0% -5% Ce02-15% Al203-5% Ba0-5% Mn02-25% SiO2)

[0052] 装填该催化剂50g于反应器中,经过250°C氢气还原后,以纯醋酸为原料保持进料量为0.5ml/min,氢气流量5000ml/min,反应温度控制在260°C,反应压力4.0Mpa,反应24h后,醋酸转化率93.5%,生成乙醇选择性94.7%。 After [0052] 50g of the catalyst packed in the reactor, 250 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.5ml / min, hydrogen flow rate of 5000ml / min, the reaction temperature is controlled at 260 ° C, the reaction pressure 4.0MPa, after 24h the reaction, the conversion rate was 93.5% acetate, 94.7% selectivity to ethanol.

[0053] 实施例9 [0053] Example 9

[0054] 按照比例称取40%硅溶胶25.0g和15%铝溶胶66.7g于0.8L中水中加热至80°C形成溶液I ;称取136.7g Cu (NO3) 2.3Η20、55.Ig Zn (NO3) 2.6Η20、19.4g Co (NO3) 2.6H20、8.5gBa (NO3) 2、重量百分比为50%Mn (NO3) 2溶液41.1g —并溶于1.0L水中,在80°C油浴中加热搅拌形成溶液2。 [0054] Weigh scale 40% silica and 15% alumina sol 25.0g 66.7g 0.8L of water was heated in 80 ° C to form a solution I; weighed 136.7g Cu (NO3) 2.3Η20,55.Ig Zn ( NO3) 2.6Η20,19.4g Co (NO3) 2.6H20,8.5gBa (NO3) 2, the weight percentage of 50% Mn (NO3) 2 solution 41.1g - and dissolved in 1.0L of water, was heated at 80 ° C in an oil bath 2 was stirred to form a solution. 配制1.0mol/L碳酸钠与1.0ml碳酸钾混合溶液为溶液3。 Formulated 1.0mol / L sodium carbonate and potassium carbonate solution is a solution of 1.0ml 3. 溶液2和溶液3同时滴加至溶液I中,保持pH为7.5左右得到沉淀物,过滤得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, to keep the pH of about 7.5 to give a precipitate was filtered to give a precipitate. 沉淀物经过干燥,焙烧,成型得到催化剂9 (以重量百分比计为45%Cu0-15%Zn0%-5%Co0-10%Al203-5%Ba0-10%Mn02-10%Si02) The precipitate was dried, calcined, obtained by molding the catalyst 9 (in percent by weight 45% Cu0-15% Zn0% -5% Co0-10% Al203-5% Ba0-10% Mn02-10% Si02)

[0055] 装填该催化剂40g于反应器中,经过270°C氢气还原后,以重量百分比50%醋酸乙醇溶液为原料保持进料量为0.6ml/min,氢气流量4000ml/min,反应温度控制在240°C,反应压力2.5Mpa,反应24h后,醋酸转化率95.5%,生成乙醇选择性89.2%。 After [0055] 40g of the catalyst packed in the reactor, 270 ° C after reduction with hydrogen, 50% by weight ethanol solution of acetic acid as the raw material feed amount is held 0.6ml / min, hydrogen flow rate of 4000ml / min, controlling the reaction temperature 240 ° C, the reaction pressure is 2.5Mpa, the reaction after 24h, acetic acid 95.5% conversion, 89.2% selectivity to ethanol.

[0056]实施例10 [0056] Example 10

[0057] 按照比例称取175.0g40%硅溶胶于1.0L中水中加热至80°C形成溶液I ;称取212.6g Cu(NO3)2.3H20、73.5g Zn (NO3) 2.6Η20、38.8g Co (NO3) 2.6H20、17.1g Ba (NO3) 2、102.9g Al(NO3)3.9Η20、重量百分比为50%Mn (NO3) 2 溶液41.2g—并溶于1.0L 水中,在80°C油浴中加热搅拌形成溶液2。 [0057] Weigh scale 1.0L 175.0g40% silica sol in water and heated to 80 ° C to form a solution I; weighed 212.6g Cu (NO3) 2.3H20,73.5g Zn (NO3) 2.6Η20,38.8g Co ( NO3) 2.6H20,17.1g Ba (NO3) 2,102.9g Al (NO3) 3.9Η20, the weight percentage of 50% Mn (NO3) 2 was dissolved in 1.0L of water and 41.2g-, at 80 ° C in an oil bath 2 was heated with stirring to form a solution. 以17%氨水为溶液3。 17% aqueous ammonia solution 3. 溶液2和溶液3同时滴加至溶液I中,保持PH为10左右得到沉淀物,蒸发掉液体得到沉淀物。 2 and 3 while the solution was added dropwise to solution I, PH maintained about 10 to give a precipitate, the liquid was evaporated to give a precipitate. 将沉淀物干燥,焙烧得到催化剂10(以重量百分比计为35%Cu0-10%Zn0%-5%Co0-7%Al203-5%Ba0-3%Mn02-35%Si02) The precipitate was dried and calcined to obtain a catalyst 10 (in percent by weight 35% Cu0-10% Zn0% -5% Co0-7% Al203-5% Ba0-3% Mn02-35% Si02)

[0058] 装填该催化剂50g于反应器中,经过220°C氢气还原后,以纯醋酸为原料保持进料量为0.5ml/min,氢气流量4000ml/min,反应温度控制在250°C,反应24h后,醋酸转化率92.5%,生成乙醇选择性90.2%。 After [0058] 50g of the catalyst packed in the reactor, 220 ° C after reduction with hydrogen to pure acetic acid as the raw material feed amount is held 0.5ml / min, hydrogen flow rate of 4000ml / min, the reaction temperature is controlled at 250 ° C, for 24h after conversion of 92.5% acetic acid, 90.2% selectivity to ethanol.

[0059] 通过以上实施例可以看出,采用该方法所提供的催化剂及工艺条件,醋酸单程转化率达95%,生成乙醇选择高,反`应条件容易达到,实现了较好的技术效果。 [0059] As can be seen by the above embodiments, the catalyst and process conditions using the provided methods, the one-way conversion rate of 95% acetic acid, choose high ethanol production, conditions should be easy to achieve the anti-`, achieve a better technical effect.

Claims (7)

1.一种由醋酸制备工业乙醇的方法,包括原料及催化剂,原料为醋酸和氢气,其特征在于催化剂采用Cu基催化剂,所述Cu基催化剂以重量百分比计由以下组分构成:15.0~40.0%Cu或其氧化物,10.0~25.0%Ζη或其氧化物,1.0~10.0%Μη或其氧化物,1.0~15.0%A1203,15.0 ~40%Si02,0.5 ~5.0% 选自Co、Ce、La、Mg、Ba 或其氧化物中的至少一种;将Cu基催化剂装填于反应器中,经220~270°C氢气还原后,将氢气与醋酸以摩尔比10~50:1进料,原料与催化剂接触,在反应温度为180~300°C,反应压力为0.5~6.0MPa,反应时间24h,醋酸质量空速为0.1~0.51 1的条件下,反应生成乙醇和水,通过产物分离得到乙醇产品。 1. A process for the preparation of industrial ethanol acetic acid, and a catalyst material comprising, as a raw material and hydrogen acetic acid, wherein the catalyst is a Cu based catalyst, the Cu-based catalyst composed of in weight percent of the following components: 15.0 to 40.0 % Cu or an oxide, 10.0 ~ 25.0% Ζη or an oxide thereof, 1.0 ~ 10.0% Μη or an oxide thereof, 1.0 ~ 15.0% A1203,15.0 ~ 40% Si02,0.5 ~ 5.0% is selected from Co, Ce, La , Mg, Ba or at least one oxide; Cu based catalyst loaded in the reactor, by 220 ~ 270 ° C after reduction with hydrogen, hydrogen gas and acetic acid in a molar ratio of 10 to 50: 1 feed, feed contacted with the catalyst at a reaction temperature of 180 ~ 300 ° C, the reaction pressure 0.5 ~ 6.0MPa, reaction time 24h, acetic acid under the conditions of weight hourly space velocity of 0.1 to 0.51 to 1, the reaction of ethanol and water to give the product is isolated by ethanol product.
2.根据权利要求1所述一种由醋酸制备工业乙醇的方法,其特征在于:反应温度为220~260°C ;反应压力为1.0~4.0MPa0 2. The method of claim 1, which further wherein the industrial preparation of ethanol by the method of acetic acid: reaction temperature of 220 ~ 260 ° C; reaction pressure is 1.0 ~ 4.0MPa0
3.根据权利要求1所述一种由醋酸制备工业乙醇的方法,其特征在于:醋酸的质量空速为0.1~0.41 1 ;氢气与醋酸的摩尔比为20~40:1。 The method for industrial preparation of ethanol from acetic acid according to claim 1, wherein: acetic mass space velocity of from 0.1 to 0.41 1; molar ratio of hydrogen to acetic acid is from 20 to 40: 1.
4.根据权利要求1或3所述一种由醋酸制备工业乙醇的方法,其特征在于:原料中醋酸以纯醋酸或醋酸溶液的形式进料,醋酸的浓度以重量百分比计为50~100%,进料量为0.2 ~0.6ml/min,氢气流量3500 ~5000ml/min。 According to claim 1 or 3, which further wherein the industrial preparation of ethanol by the method of acetic acid: acetic acid as the raw material of pure acetic acid or acetic acid in the feed solution, the concentration of acetic acid in weight percent of 50 to 100%, feed rate of 0.2 ~ 0.6ml / min, hydrogen flow rate of 3500 ~ 5000ml / min.
5.根据权利要求1所述一种由醋酸制备工业乙醇的方法,其特征在于:所述Cu基催化剂以重量百分比计由以下组分构成:15.0~35.0%Cu或其氧化物;15~20.0%Ζη或其氧化物;1.0 ~10.0%Μη 或其氧化物;5.0 ~15.00Ml2O3 ; 15.0 ~30.0%Si02 ;1.0 ~5.0%选自Co、Ce、La、Mg、Ba或其氧化物中的至少一种。 5. The method of claim 1, which further wherein the industrial preparation of ethanol by the method of acetic acid: the Cu-based catalyst composed of in weight percent of the following components: 15.0 ~ 35.0% Cu or an oxide thereof; 15 to 20.0 % Ζη or an oxide thereof; 1.0 ~ 10.0% Μη or an oxide thereof; 5.0 ~ 15.00Ml2O3; 15.0 ~ 30.0% Si02; 1.0 ~ 5.0% is selected from Co, Ce, La, Mg, Ba, or an oxide of at least one kind.
6.根据权利要求1所述一种由醋酸制备工业乙醇的方法,其特征在于:所述Cu基催化剂的制备包括以下步骤:将40%硅溶胶和15%铝溶胶于1.0-1.2L中水中加热至70-85°C形成溶液I,或称取一定量Al2O3加入到1.0L中水中加热至80°C形成溶液I ;将所需量的选自含Cu、Zn、Co、Ce、La、Mg、Ba、Al和Mn可溶性物溶于1.0L水中,在75_80°C油浴中加热搅拌形成溶液2 ;以1.0mol/L碳酸钠水溶液或1.0mol/L碳酸钾水溶液或氨水为溶液3 ;溶液2和溶液3同时滴入溶液I中并控制pH值6.5-10得到沉淀物,滴加完全后经过滤、洗涤、干燥、焙烧、成型后得到Cu基催化剂。 6. The A, characterized by the process according to claim industrial preparation of ethanol acetate: preparing said Cu based catalyst comprises the steps of: 40% silica and 15% alumina sol in water in 1.0-1.2L was heated to 70-85 ° C to form a solution I, or a weighed amount of Al2O3 was added to 1.0L of water and heated to 80 ° C to form a solution I; selected from the group containing the desired amount of Cu, Zn, Co, Ce, La, mg, Ba, Al and Mn was dissolved in 1.0L of water soluble, heated at 75_80 ° C oil bath and stirred for 2 to form a solution; in 1.0mol / L aqueous sodium carbonate solution or 1.0mol / L aqueous potassium carbonate or aqueous ammonia solution is 3; 2 and 3 while the solution was added dropwise a solution of I and 6.5-10 pH control resulting precipitate was added dropwise one after filtering, washing, drying, calcination, the Cu based catalyst obtained by molding.
7.根据权利要求6所述一种由醋酸制备工业乙醇的方法,其特征在于:将所需量的选自含Cu、Zn、Co、Ce、La、Mg、Ba、Al 和Mn 可溶性物为Cu(NO3)2.3H20、Zn(NO3)2.6H20、Co (NO3) 2.6H20、Ce (NO3) 2.6H20、La (NO3) 3.6H20、Mg (NO3) 2.6H20、Ba (NO3) 2、Al (NO3) 2.9H20、重量百分比为50%Mn (NO3) 2溶液。 7. 6 one of claim wherein the industrial preparation of ethanol by the method of acetic acid: containing the desired amount of selected Cu, Zn, Co, Ce, La, Mg, Ba, Al, and Mn thereof was soluble Cu (NO3) 2.3H20, Zn (NO3) 2.6H20, Co (NO3) 2.6H20, Ce (NO3) 2.6H20, La (NO3) 3.6H20, Mg (NO3) 2.6H20, Ba (NO3) 2, Al ( NO3) 2.9H20, the weight percentage of 50% Mn (NO3) 2 solution.
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