WO2015089703A1 - 用于生产甲醇并联产c2-c4醇的方法 - Google Patents

用于生产甲醇并联产c2-c4醇的方法 Download PDF

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WO2015089703A1
WO2015089703A1 PCT/CN2013/089536 CN2013089536W WO2015089703A1 WO 2015089703 A1 WO2015089703 A1 WO 2015089703A1 CN 2013089536 W CN2013089536 W CN 2013089536W WO 2015089703 A1 WO2015089703 A1 WO 2015089703A1
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catalyst
carbon
methanol
synthesis gas
low
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French (fr)
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刘勇
朱文良
刘红超
倪友明
刘中民
孟霜鹤
李利娜
刘世平
周慧
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Dalian Institute of Chemical Physics of CAS
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8878—Chromium
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    • B01J23/84—Catalysts 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
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation 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
    • C07C29/136—Preparation 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
    • C07C29/147—Preparation 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
    • C07C29/149—Preparation 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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    • B01J23/76—Catalysts 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
    • B01J23/84—Catalysts 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
    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions

  • the present invention is in the field of catalytic chemistry and relates to a process for producing methanol in parallel to produce lower alcohols. Background technique
  • Methanol is an important chemical raw material and clean liquid fuel, mainly used as a solvent and raw materials for the preparation of formaldehyde, acetic acid, dimethyl ether, and MTG, MTO and other processes.
  • the production capacity of methanol at home and abroad has grown rapidly. From 2000 to 2008, the world's methanol production capacity increased by about 10% annually. Among them, China's methanol production capacity grew at an average annual rate of 23.5%. In 2011, China's methanol production reached 20.35 million tons. With the promotion of MTO and other technologies, it is expected that methanol production will increase in the future.
  • the medium and low pressure methanol synthesis process has been developed successively by the companies represented by British ICI Company and German Lurgi Company.
  • the medium and low pressure method can achieve high activity and high selectivity synthesis of methanol at a lower temperature (200-290 ° C) and a lower pressure (5 MPa).
  • the catalyst used is a copper catalyst (CuO/ZnO/Al 2 ). 0 3 , CuO/ZnO/Cr 2 0 3 , CuO/ZnO/MnO). Since the mid-1970s, almost all new and expanded methanol synthesis plants in the world have adopted medium and low pressure synthesis processes.
  • Low-carbon alcohol also known as C 2+ OH
  • C 2+ OH generally refers to a fatty alcohol with a carbon number of 2-6.
  • it can also be used as a gasoline additive to increase the bismuth value.
  • It is also an important basic raw material in the chemical industry.
  • One of them has a wide range of applications [Li Debao et al., Progress in Chemistry, 2004 (16) 584-592; Ge Qingjie et al., Chemical Progress, 2009 (28;) 917-921].
  • relatively concentrated systems for the synthesis of low-carbon alcohol catalysts mainly include modified methanol synthesis catalysts, Cu-Co groups and MoS 2 based catalysts [Forzatti P etc. Catal. Rev. 1991 (33) 109-168; Mahdavi V etc. Appl. Catal. A 2005 (281) 259-265].
  • An object of the present invention is to provide a process for synthesizing methanol to produce other lower alcohols (C2-C4 alcohols) by using a mixture of a lower carbon ester and a synthesis gas as a reaction material.
  • the present invention provides a process for producing methanol in parallel to produce C2-C4 alcohol, characterized in that a feed gas containing a lower carbon ester and a synthesis gas is passed through a reactor equipped with a catalyst at a reaction temperature of 150.
  • a feed gas containing a lower carbon ester and a synthesis gas is passed through a reactor equipped with a catalyst at a reaction temperature of 150.
  • the active component is copper and optionally zinc and/or aluminum.
  • the lower alcohol ester is one or more of an aliphatic ester having a total carbon number of not more than 8 (ie, a carbon number of 8 or less);
  • the polyhydric alcohol is ethanol, propanol, and butyl.
  • the active component copper is 50.0-100.0% by weight of the total weight of the catalyst in terms of CuO; zinc is 0-35.0% by weight of the total weight of the catalyst in terms of ZnO; Aluminum accounts for 0-10.0% by weight of the total weight of the catalyst in terms of A1 2 0 3 .
  • the catalyst further contains one or more of manganese, molybdenum, zirconium, chromium, iron, cerium, magnesium, nickel, calcium as an auxiliary. More preferably, the auxiliaries are manganese, chromium, iron, magnesium, nickel, most preferably manganese, iron, chromium.
  • the adjuvant is from 0 to 5.0% by weight based on the total weight of the catalyst, based on its metal oxide.
  • the catalyst is reduced with H 2 and / or synthesis gas prior to use.
  • the synthesis gas/low carbon ester molar ratio is 9 to: 1000/1 in the raw material gas, and the hydrogen/carbon monoxide molar ratio in the synthesis gas is 0.06 to 300/1.
  • the synthesis gas / lower carbon ester molar ratio is 40 to 560/1, and the hydrogen/carbon monoxide molar ratio of the synthesis gas is 0.3 to ⁇ 1.
  • the syngas also contains carbon dioxide, nitrogen and formamidine, and carbon dioxide, nitrogen and formamidine comprise from 3 to 13% by mole of the synthesis gas.
  • the reaction temperature is 180 to 300 ° C
  • the reaction pressure is 1.0 to 10.0 MPa
  • the reaction volume space velocity is 400-30000 mlg - 1
  • the lower ester Mass airspeed is 0.1 ⁇ 1.0h—
  • Advantageous effects of the present invention include, but are not limited to: providing a new reaction process for synthesizing methanol in parallel with a catalyst of a low-carbon ester and syngas to produce ethanol, propanol,
  • the addition of butanol, a lower ester promotes catalytic activity and does not affect catalyst life.
  • the ratio of each lower alcohol can be adjusted by changing the reaction conditions, which greatly improves product flexibility and market adaptability.
  • the method of the invention utilizes a co-feed of a low-carbon ester and a syngas as a reaction raw material to synthesize methanol to produce another low-carbon alcohol in parallel, wherein a raw material gas containing a lower-carbon ester and a synthesis gas is passed through a reactor equipped with a catalyst in the reaction.
  • the active component in the catalyst is copper, and may also contain zinc and/or aluminum.
  • the lower carbon ester is one or a mixture of any of several aliphatic esters having a total carbon number of not more than 8.
  • the lower carbon ester is ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate.
  • Butyl propionate a mixture of ester, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate or a mixture of any of the following;
  • the lower alcohol is one of methanol, ethanol, propanol, butanol or A variety.
  • the active component copper is 50.0-100.0% by weight based on the total weight of the catalyst, and the promoter zinc is 0-35.0% by weight based on the total weight of the catalyst;
  • the aluminum agent is 0-10.0% by weight based on the total weight of the catalyst, based on the metal oxide.
  • the catalyst may further contain a composition of one or any of manganese, molybdenum, zirconium, chromium, iron, cerium, magnesium, nickel, calcium, and more preferably, the auxiliary agent is manganese. Chromium, iron, magnesium, and nickel are most preferably manganese, iron, and chromium. It is 0-5.0 wt% based on the total weight of the catalyst, based on the metal oxide (e.g., MnO, Cr 2 O 3 , Fe 2 O 3 , MgO, NiO, etc.).
  • the metal oxide e.g., MnO, Cr 2 O 3 , Fe 2 O 3 , MgO, NiO, etc.
  • the synthesis gas/low carbon ester molar ratio is 9 to 1000/1, and the hydrogen/carbon monoxide molar ratio in the synthesis gas is 0.06 to 300/1.
  • the syngas may also contain carbon dioxide, nitrogen and formamidine, which may comprise from 3 to 13% by mole of the synthesis gas.
  • the synthesis gas/low carbon ester molar ratio is 40 to 560/1, and the hydrogen/carbon monoxide molar ratio in the synthesis gas is 0.3 to: 100/1.
  • the reaction conditions are: a reaction temperature of 180 to 300 ° C, a reaction pressure of 1.0 to 10.0 MPa, a reaction volume space velocity of 400 to 30 000 mlg 1 ⁇ 1 , and a low carbon ester mass space velocity of 0.1 to: 1.Oh-
  • the catalyst of the present invention (also referred to as a copper-based catalyst) is preferably prepared by a coprecipitation method, and includes the following steps:
  • step a) adding a solution containing Cu 2+ and optionally Zn 2+ and/or Al 3+ ions to a precipitant solution at 25-60 ° C, stirring the resulting precipitate to homogeneity, and obtaining a precipitate having a pH of 7.0- 1); b) the precipitate obtained in step a) is aged for 5 to 60 hours, dried at 80-160 ° C and calcined at 240-500 ° C to obtain a calcined sample;
  • step b) optionally, the calcined sample obtained in step b) is placed in a salt solution containing one or more of the components manganese, molybdenum, zirconium, chromium, iron, strontium, magnesium, nickel, calcium
  • the catalyst is obtained by dipping one or more times, drying after drying at 80-160 ° C, and calcination at 240-500 ° C.
  • the main advantages of the present invention are mainly: under the condition of co-feeding of low-carbon ester and syngas, in one One reactor synthesizes methanol to produce low-carbon alcohol in parallel (the ratio of methanol and low-carbon alcohol is adjustable), the addition of low-carbon ester promotes catalytic activity and does not affect the life of the catalyst, greatly improving product flexibility and Market adaptability.
  • the invention is described in detail below by way of examples, but the invention is not limited to the examples.
  • the obtained precipitate was dried in an oven at 120 ° C for 24 hours. After drying, the sample was placed in a muffle furnace, heated to 400 ° C at a heating rate of rC / mm, and calcined for 5 hours to obtain a calcined sample.
  • This catalyst is referred to as CAT1.
  • the water was diluted with 72.52 g of concentrated ammonia (25-28%).
  • the aqueous ammonia solution was vigorously stirred at room temperature, and then the mixed metal nitrate aqueous solution was slowly added to the aqueous ammonia solution for about 60 minutes.
  • the pH of the precipitate was adjusted to 10.0 with an aqueous ammonia solution, and after stirring for 200 mm, it was aged for 36 hours.
  • the precipitate was washed with deionized water to neutrality and centrifuged.
  • the obtained precipitate was dried in an oven at 120 ° C for 24 hours. After drying, the sample was placed in a muffle furnace, heated to 400 ° C at a heating rate of rC / mm, and calcined for 5 hours to obtain a calcined sample.
  • This catalyst is referred to as CAT3.
  • Adjusting the precipitation with aqueous ammonia solution The pH was adjusted to 10.0, and after stirring for 200 mm, it was aged for 36 hours. The precipitate was washed with deionized water to neutrality and centrifuged. The obtained precipitate was dried in an oven at 120 ° C for 24 hours. After drying, the sample was placed in a muffle furnace, heated to 400 ° C at a heating rate of rC / mm, and calcined for 5 hours to obtain a calcined sample.
  • the rest of the catalysts CAT2 and CAT5 ⁇ 10 were prepared similarly to CAT3 and CAT4.
  • the relationship between the specific preparation conditions of the catalyst and the numbering is shown in Table 1.
  • the catalyst composition determined by XR (X-ray fluorescence spectroscopy, PANalytical, The Netherlands) is shown in Table 2.
  • the reaction volume space velocity in the present invention is defined as the volumetric flow rate of the reaction feedstock (in standard conditions) entering the reaction system per hour divided by the mass of the catalyst. Expressed in GHSV, the unit is mlg - 10 g of 20-40 mesh of the above catalyst is charged into the fixed bed reactor thermostat. Before the reaction, the catalyst was subjected to on-line reduction, the reduction temperature was 260 ° C, the pressure was 0.1 MPa, the reducing gas was 5% H 2 + 95% N 2 , and the reduction time was 24 h.
  • FID column HP-PLOT-Q 19091P-Q04, 30m x 0.32mm (inside diameter), 20 ⁇ film thickness
  • Carrier gas helium, 2 ml/min
  • Oven temperature 50°C-240°C, 10°C/min
  • TCD column carbon molecular sieve column, TDX-01 2m X 2mm (inside diameter)
  • Carrier gas helium, 35ml/min
  • Oven temperature 50°C-240°C, 10°C/min
  • Catalyst CAT4 is co-fed with butyl acetate (C 6 H 12 0 2 ) and syngas (volume composition 87.72% 3 ⁇ 4/11.70% CO/0.58% C 6 H 12 O 2 ) at different temperatures.
  • the reaction performance of C2 ⁇ C4 lower alcohols produced in parallel is shown in Table 4.
  • Catalyst CAT7 was prepared by co-feeding propyl butyrate (C 7 H 14 0 2 ) gas (volume composition 86.20% CO/12.93% CO/0.87% C 7 H 14 O 2 ) under different pressures.
  • the reaction performance of the parallel production of lower alcohols is shown in Table 5.
  • the invention has the advantages that, by using the copper-based catalyst of the invention, the synthesis of methanol and the co-production of C2-C4 lower alcohol are achieved by adding a small amount of a lower ester (the total carbon number of the lower carbon ester is not higher than 8) in the synthesis gas, and The addition of the lower carbon ester promotes the catalytic activity (increased single pass conversion of carbon monoxide) without affecting the catalyst life (the catalyst life is similar to that of the single synthesis gas hydrogenation to methanol).
  • the product composition can be easily regulated by changing the syngas/lower ester feed ratio for flexible operation and greater economics.

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Abstract

　本发明涉及一种以低碳酯与合成气共进料作为反应原料来生产甲醇并联产C2-C4醇的方法，其中将含有低碳酯和合成气的原料气，通过装有催化剂的反应器，在反应温度150〜350°C、反应压力0.1〜20.0MPa、反应体积空速为100〜40000mlg-1h-1、低碳酯质量空速为0.01〜3.0h-1的条件下生产多级醇；所述催化剂的活性组分为铜以及任选的锌和/或铝。本发明方法在使用低碳酯和合成气共进料的条件下，在一个反应器中在一种催化剂上合成甲醇的同时联产一定量C2〜C4醇，产物醇之间的比例可调。

Description

用于生产甲醇并联产 C2-C4醇的方法
技术领域
本发明属于催化化学领域， 涉及一种用于生产甲醇并联产低级醇的方 法。 背景技术
甲醇是一种重要的化工原料和清洁液体燃料， 主要作为溶剂和制备甲 醛、 乙酸、 二甲醚， 以及 MTG、 MTO等过程的原料。 近年来， 国内外甲 醇的生产能力在急速地增长。 2000年至 2008年世界甲醇产能年均增长约 10%, 其中， 我国甲醇产能年均增长则高达 23.5%。 2011年我国甲醇产量 达到 2035万吨， 随着 MTO等技术的推广， 预计今后甲醇产量还会增长。 随着生物柴油和燃料电池等新兴技术的发展， 尤其是随着能源结构的改 变， 甲醇已发展成为重要的石油替代能源之一。 我国于 2009 年颁布了燃 料甲醇以及 M85 甲醇汽油的国家标准， 因此， 在不远的将来， 全世界对 甲醇的需求量会越来越大。
工业甲醇合成工艺分为高压法和中低压法 [Lee S Methanol synthesis technology岡. Boca Raton, Florida, USA: CRC Press, Inc., 1990; Ertl G. etc Handbook of Heterogeneous Catalysis岡. Maiden, MA, USA: John Wiley & Sons, Inc., 2008: 2920-2949]。高压法由德国 BASF公司于 1923年实现工业 化， 该方法采用锌铬氧化物为催化剂， 在 30-35MPa， 300-400°C条件下， 一氧化碳和氢气反应合成甲醇。 随着原料气净化技术的发展， 尤其是脱硫 技术的进歩， 以英国 ICI公司和德国 Lurgi公司为代表的企业相继开发了 中低压甲醇合成工艺。 中低压法可以在较低的温度（200-290°C )和较低的 压力 （5MPa) 下实现甲醇的高活性、 高选择性合成， 所用的催化剂为铜 系催化剂 （CuO/ZnO/Al203, CuO/ZnO/Cr203, CuO/ZnO/MnO )。 上世纪 70 年代中期以后， 世界上新建和扩建的甲醇合成装置几乎都采用了中低压合 成工艺。
我国甲醇工业始于 20世纪 50年代， 开始利用国外技术采用高压法合 成甲醇，到 60年代末期开始自主研发中低压甲醇催化剂，最早开发了 C207 催化剂用于联醇工艺。 80年代开发的 C301和 C302催化剂广泛应用于国 内甲醇合成装置。
低碳醇 （也称 C2+OH)， 一般指碳数为 2-6的脂肪醇， 除用作液体燃 料外， 还可作为汽油添加剂以增加辛垸值， 同时还是化工领域重要的基础 原料之一， 具有广泛的应用领域 [李德宝等， 化学进展， 2004 (16) 584-592; 葛庆杰等， 化工进展， 2009 (28；) 917-921]。 目前对合成低碳醇催化剂研究 相对比较集中的体系主要有改性的甲醇合成催化剂、 Cu-Co 基以及 MoS2 基催化剂等 [Forzatti P etc. Catal. Rev. 1991 (33) 109-168; Mahdavi V etc. Appl. Catal. A 2005 (281) 259-265]。
由于目前国内甲醇市场产能过剩， 如果可以在合成甲醇的同时联产一 部分其他低碳醇， 则可以提高产品多样性和经济性， 根据市场需求调节甲 醇、 低碳醇比例， 提高产品的灵活性和装置操作机动性， 对开发新型煤化 工产业有着重要的现实意义。本领域需要开发一种低碳酯与合成气共进料 条件下合成甲醇并联产其他低碳醇的方法。 发明内容
本发明的目的在于提供一种利用低碳酯与合成气共进料作为反应原 料来合成甲醇并联产其他低碳醇 (C2-C4醇)的方法。
为此， 本发明提供一种用于生产甲醇并联产 C2-C4醇的方法， 其特征 在于， 将含有低碳酯和合成气的原料气， 通过装有催化剂的反应器， 在反 应温度 150〜350°C、反应压力 0.1〜20.0MPa、反应体积空速为 100〜40000 mlg-1^1, 低碳酯质量空速为 0.01〜3.0h— 1的条件下生产多级醇； 所述催化 剂的活性组分为铜以及任选的锌和 /或铝。
在一个优选实施方式中， 所述低碳酯为总碳数不高于 8 (即碳数 8以 下） 的脂肪族酯中的一种或几种； 所述多级醇为乙醇、 丙醇和丁醇中的一 种或多种以及甲醇。
在一个优选实施方式中， 在所述催化剂中， 活性组分铜以 CuO计占 所述催化剂总重量的 50.0-100.0wt%； 锌以 ZnO计占所述催化剂总重量的 0-35.0wt%; 铝以 A1203计占所述催化剂总重量的 0-10.0wt%。 在一个优选实施方式中， 所述催化剂还含有锰、 钼、 锆、 铬、 铁、 钡、 镁、 镍、 钙中的一种或多种作为助剂。 更优选地， 所述助剂为锰、 铬、 铁、 镁、 镍， 最优选为锰、 铁、 铬。 优选地， 所述助剂以其金属氧化物计占所 述催化剂总重量的 0-5.0 wt%。
在一个优选实施方式中， 所述催化剂在使用前用 H2和 /或合成气进行 还原。
在一个优选实施方式中， 在所述原料气中， 合成气 /低碳酯摩尔比为 9〜： 1000/1，所述合成气中氢气 /一氧化碳的摩尔比为 0.06〜300/1。优选地， 合成气 /低碳酯摩尔比为 40〜560/1，所述合成气中氢气 /一氧化碳的摩尔比 0.3〜丽 1。
在一个优选实施方式中，所述合成气中还含有二氧化碳、氮气和甲垸， 并且二氧化碳、 氮气和甲垸占所述合成气的摩尔百分含量为 3〜13%。
在一个优选实施方式中，所述反应温度为 180〜300°C，所述反应压力 为 1.0〜10.0MPa， 所述反应体积空速为 400-30000 mlg-1!^ , 并且所述低碳 酯质量空速为 0.1〜1.0h—
本发明的有益效果包括但不限于： 提供了一种新的反应工艺， 在低碳 酯和合成气共进料条件下， 在一个反应器一种催化剂上合成甲醇并联产乙 醇、丙醇、丁醇，低碳酯的加入促进了催化反应活性且不影响催化剂寿命。 通过改变反应条件可以调节各低级醇的比例， 大大提高了产品灵活性和对 市场适应性。 具体实施方式
本发明方法利用低碳酯与合成气共进料作为反应原料来合成甲醇并 联产其他低碳醇， 其中将含有低碳酯和合成气的原料气， 通过装有催化剂 的反应器， 在反应温度 150〜350°C、 反应压力 0.1〜20.0MPa、 反应体积 空速为 100〜40000 mlg 1^1,低碳酯质量空速为 0.01〜3.0h— 1的条件下生产 多级醇； 所述催化剂中活性组分为铜， 也可以含有助剂锌和 /或助剂铝。
所述低碳酯为总碳数不高于 8的脂肪族酯中的一种或任意几种的混合 物。 例如， 所述低碳酯为甲酸乙酯、 甲酸丙酯、 甲酸丁酯、 乙酸甲酯、 乙 酸乙酯、 乙酸丙酯、 乙酸丁酯、 丙酸甲酯、 丙酸乙酯、 丙酸丙酯、 丙酸丁 酯、 丁酸甲酯、 丁酸乙酯、 丁酸丙酯、 丁酸丁酯中的一种或任意几种的混 合物； 低碳醇为甲醇、 乙醇、 丙醇、 丁醇中的一种或多种。
所述催化剂中， 优选地， 活性组分铜以金属氧化物计， 占催化剂总重 量的 50.0-100.0wt%； 助剂锌以金属氧化物计， 占催化剂总重量的 0-35.0wt%; 助剂铝以金属氧化物计， 占催化剂总重量的 0-10.0wt%。
所述催化剂中， 还可以含有助剂锰、 钼、 锆、 铬、 铁、 钡、 镁、 镍、 钙中的一种或任意几种的组合物， 更优选地， 所述助剂为锰、铬、铁、镁、 镍， 最优选为锰、 铁、 铬。 其以金属氧化物 （例如 MnO， Cr203， Fe203， MgO, NiO等） 计， 占催化剂总重量的 0-5.0 wt%。
所述催化剂在反应前，可以先用 H2和 /或合成气进行还原。用 1〜100% H2或合成气 （H2/CO=0.5〜50) 在温度 180〜350°C、 压力 0.1〜5.0MPa条 件下， 对其进行还原处理 5〜60小时。
所述原料气中， 合成气 /低碳酯摩尔比为 9〜1000/1， 所述合成气中氢 气 /一氧化碳的摩尔比为 0.06〜300/1。
所述合成气中还可以含有二氧化碳、 氮气和甲垸， 其占合成气的摩尔 百分含量为 3〜13%。
所述原料气中， 合成气 /低碳酯摩尔比为 40〜560/1， 所述合成气中氢 气 /一氧化碳的摩尔比 0.3〜： 100/1。
优选反应条件为：反应温度为 180〜300°C，反应压力为 1.0〜10.0MPa， 反应体积空速为 400-30000 mlg 1^1 , 低碳酯质量空速为 0.1〜： l .Oh—
本发明所述的催化剂 （也称为铜基催化剂） 优选采用共沉淀法制备， 包括以下歩骤：
a) 将含有 Cu2+和任选的 Zn2+和 /或 Al3+离子的溶液加入 25-60 °C的沉 淀剂溶液中， 搅拌所得沉淀物至均匀， 所得沉淀物 pH值为 7.0-10.0; b)歩骤 a)中所得沉淀物经 5-60小时老化、 80-160°C干燥和 240-500 °C 焙烧处理， 得到焙烧样品；
c) 任选地， 将歩骤 b) 中所得的焙烧样品置于含有组分锰、 钼、 锆、 铬、铁、钡、镁、镍、钙中的一种或几种金属的盐溶液中浸渍一次或多次， 浸渍完成后经 80-160°C干燥、 240-500 °C焙烧得到所述催化剂。
本发明的主要优势主要在于： 在低碳酯与合成气共进料条件下， 在一 个反应器一种催化剂上合成甲醇并联产低碳醇（甲醇、 低碳醇比例可调）， 低碳酯的加入促进了催化反应活性且不影响催化剂寿命， 大大提高了产品 灵活性和对市场适应性。 下面通过实施例详述本发明， 但本发明并不局限于这些实施例。
实施例 1: 催化剂制备
1 ) 100%CuO催化剂的制备
将 121g Cu(N03)2-3H20溶于 2000ml去离子水中，用 1500ml去离子水 稀释 68.0g浓氨水 （25-28%)。 在室温下剧烈搅拌氨水溶液， 然后将该金 属硝酸盐水溶液缓慢加入氨水溶液中， 加入时间 60min左右。 用氨水溶液 调节沉淀 pH值到 10.0， 继续搅拌 200mm之后， 老化 36h。 将沉淀用去离 子水洗涤至中性， 离心分离。 所得沉淀在 120°C烘箱中干燥 24h， 干燥后 样品置于马弗炉中， 以 rC/mm的升温速率升温到 400°C， 焙烧 5h， 得到 焙烧后的样品。 此催化剂记为 CAT1。
2) 85%CuO/10%ZnO/5%Al2O3催化剂的制备
将 102.85g Cu(N03)2-3H20 、 12.00g Ζη(Ν03)2·6Η20 、 14.71g Α1(Ν03)3·9Η20溶于 2000ml去离子水中， 用 1500ml去离子水稀释 72.52g 浓氨水 （25-28%)。 在室温下剧烈搅拌氨水溶液， 然后将混合金属硝酸盐 水溶液缓慢加入氨水溶液中， 加入时间 60min左右。用氨水溶液调节沉淀 pH值到 10.0， 继续搅拌 200mm之后， 老化 36h。 将沉淀用去离子水洗涤 至中性， 离心分离。 所得沉淀在 120°C烘箱中干燥 24h， 干燥后样品置于 马弗炉中， 以 rC/mm的升温速率升温到 400°C， 焙烧 5h， 得到焙烧后的 样品。 此催化剂记为 CAT3。
3 ) 75%CuO/13%ZnO/5%Al203/l%MnO/l%NiO催化剂的制备 将 96.80g Cu(N03)2-3H20 ， 15.60g Ζη(Ν03)2·6Η20 ， 14.71g Α1(Ν03)3·9Η20溶于 2000ml去离子水中， 用 1500ml去离子水稀释 72.62g 浓氨水 （25-28%)。 在室温下剧烈搅拌氨水溶液， 然后将混合金属硝酸盐 水溶液缓慢加入氨水溶液中， 加入时间 60min左右。用氨水溶液调节沉淀 pH值到 10.0， 继续搅拌 200mm之后， 老化 36h。 将沉淀用去离子水洗涤 至中性， 离心分离。 所得沉淀在 120°C烘箱中干燥 24h， 干燥后样品置于 马弗炉中， 以 rC/mm的升温速率升温到 400°C， 焙烧 5h， 得到焙烧后的 样品。再将 1.41g Mn(N03)2'4H20， 1.36g Ni(N03)2-4H20溶于 50ml去离子 水， 采用浸渍法把锰和镍水溶液担载到焙烧后的样品中， 80°C蒸发掉多余 的溶剂。 120°C烘箱中干燥 24h， 干燥后样品置于马弗炉中， 以 rC/mm的 升温速率升温到 400°C， 焙烧 3h， 得到催化剂样品。 此催化剂记为 CAT4 其余催化剂 CAT2和 CAT5~10的制备与 CAT3和 CAT4类似。催化剂 具体制备条件与编号的关系见表 1。 XR (X-射线荧光光谱， 荷兰帕纳科 公司） 测定的催化剂组成见表 2。
表 1: 催化剂制备
Figure imgf000008_0001
表 2 ： XRF测定的催化剂组成
Figure imgf000009_0001
实施例 2: 催化剂评价
本发明中的反应体积空速定义为反应原料（标准状况下）每小时进入 反应系统的体积流量除以催化剂的质量。 以 GHSV表示， 单位为 mlg— 将 10g 20-40目上述催化剂装填入固定床反应器恒温区。 反应前， 对 催化剂进行在线还原， 还原温度为 260°C， 压力 O.lMPa, 还原气体为 5% H2+95% N2， 还原时间 24h。
还原结束后， 用 N2吹扫管路和反应器内残余的 H2， 然后把气体切换 为一定组成的合成气并充压， 调节质量流量计到指定流量 （标准状况）， 设置低碳酯高压进料泵到指定流速， 当温度和压力稳定后开始反应。 产物 在线分析， 1小时取样一次。 从反应器出口到气相色谱十通阀入口， 所有 管线以及背压阀都进行加热保温。 产物的分析方法
色谱： Agilent 7890A
FID色谱柱： HP-PLOT-Q 19091P-Q04, 30m x 0.32mm (内径)， 20μπι 膜厚
载气： 氦气， 2 ml/min
柱箱温度： 50°C-240°C， 10°C/min
240°C保持 15min
进样口： 分流 （50:1 ); 温度： 250°C 检测器： FID; 温度： 300°C
TCD色谱柱： 碳分子筛柱， TDX-01 2m X 2mm (内径）
载气： 氦气， 35ml/min
柱箱温度： 50°C-240°C， 10°C/min
240°C保持 15min
进样口： 隔垫吹扫进样口； 温度： 250°C
检测器： TCD; 温度： 300°C
1 ) 在不同组成的上述催化剂上， 以丙酸乙酯 (C5H1Q02)与合成气 （体 积组成为 70.59%¾/23.53%CO/3.52%CO2+N2/2.36%C5H1QO2) 共进料制取 甲醇并联产 C2 C4低碳醇的反应性能见表 3。
反应条件： 反应温度 230°C, 反应压力 4.0MPa, 原料气组成摩尔比 H2/CO/CO2+N2/C5H10O2=30/10/1.5/l(70.59%¾/23.53%CO/3.52%CO2+N2/2. 36%C5H10O2), 总体积空速 GHSV=2792mlg— ― 低碳酯质量空速 WHSV m 酸乙酷 =0.3h 1 表 3: 不同催化剂上丙酸乙酯与合成气共进料制取甲醇并联产 C2~C4 低碳醇的反应性能
Figure imgf000010_0001
2) 催化剂 CAT4在不同温度下以乙酸丁酯 (C6H1202)与合成气 （体积 组成为 87.72%¾/11.70%CO/0.58%C6H12O2)共进料制取甲醇并联产 C2~C4 低碳醇的反应性能见表 4 反应条件： 6.5MPa, H2/CO/C6H1202=l 50/20/1 (87.72%H2/11.70%CO /0.58%C6H12O2), GHSV=26635mlg"1h"1, WHSV 乙酸丁酷 =0.811 表 4: 反应温度对 CAT4催化剂在乙酸丁酯与合成气共进料制取甲醇 并联产 C2 C4低碳醇中的反应性能的影响
Figure imgf000011_0001
3 ) 催化剂 CAT7在不同压力下以丁酸丙酯 (C7H1402)成气 （体积组成 为 86.20%CO/12.93%CO/0.87%C7H14O2) 共进料制取甲醇并联产低碳醇的 反应性能见表 5。
反 应 条 件 ： 250°C, H2/CO/C7H14O2=100/15/l (86.20%CO/12.93%CO/0.87%C7H14O2), GHSV=9903mlg" ^-1, WHSV 丁酸丙酷 =0.5 ι
表 5: 反应压力对催化剂在 CAT7丁酸丙酯与合成气共进料制取甲醇 并联产 C2 C4低碳醇中的反应性能的影响
Figure imgf000011_0002
4 ) 不同催化剂、 不同反应条件下以低碳酯与合成气共进料制取甲醇 并联产 C2 C4低碳醇的反应性能见表 6。 表 6： 不同催化剂和反应条件下以低碳酯与合成气共进料制取甲醇并联产低碳醇的反应性能
Figure imgf000012_0001
根据以上实施例及数据可得出如下结论：
在特定的催化剂上， 一个反应器中， 适当的反应条件下， 一定量的低 碳酯（低碳酯质量空速为 0.01〜3.0h— 优选为 O. l l .Oh—1 )与合成气（氢 气与碳氧化物） 共进料， 会有效地生成包括甲醇和 C2-C4 低级醇在内的 多级醇。 通过调整合成气 /低碳酯比例， 可以方便的调控产物 C1-C4低级 醇之间的比例， 而不影响过程的催化效率， 进而根据市场变化调节产品产 量， 提高企业应对市场风险的能力和工业装置的操作灵活性。
本发明的优势在于， 使用本发明的铜基催化剂， 通过在合成气中加入 少量低碳酯（低碳酯总碳数不高于 8)实现了合成甲醇和联产 C2-C4低级 醇， 且低碳酯的加入促进了催化反应活性 （提高了一氧化碳单程转化率） 又不影响催化剂寿命 （催化剂寿命与单独合成气加氢制甲醇寿命相仿）。 通过改变合成气 /低碳酯进料比例可方便的调控产物组成， 实现灵活操作 和更大的经济性。
应当指出， 对于本技术领域的专业技术人员， 在不脱离本发明技术原 理的前提下， 是能够实现对这些实施例的多种修改的， 而这些修改也应视 为本发明应该保护的范围内。

Claims

权 利 要 求
1. 一种用于生产甲醇并联产 C2-C4醇的方法， 其特征在于， 将含有 低碳酯和合成气的原料气， 通过装有催化剂的反应器， 在反应温度 150〜 350°C、 反应压力 0.1〜20.0MPa、 反应体积空速为 100〜40000 mlg"1^1, 低碳酯质量空速为 0.01〜3.0h— 1的条件下生产甲醇并联产 C2-C4醇； 所述 催化剂的活性组分为铜以及任选的锌和 /或铝。
2. 根据权利要求 1 所述的方法， 其特征在于， 所述低碳酯为总碳数 不高于 8的脂肪族酯中的一种或几种。
3. 根据权利要求 1 所述的方法， 其特征在于， 在所述催化剂中， 活 性组分铜以 CuO计占所述催化剂总重量的 50.0-100.0wt%；锌以 ZnO计占 所述催化剂总重量的 0-35.0wt%； 铝以 A1203计占所述催化剂总重量的 0-10.0wt%。
4. 根据权利要求 1所述的方法， 其特征在于， 所述催化剂还含有锰、 钼、 锆、 铬、 铁、 钡、 镁、 镍、 钙中的一种或多种作为助剂。
5. 根据权利要求 4所述的方法， 其特征在于， 所述催化剂助剂是锰、 铬、 铁、 镁、 镍中的一种或多种。
6. 根据权利要求 5所述的方法， 其特征在于， 所述助剂以其金属氧 化物计占所述催化剂总重量的 0-5.0 wt%。
7. 根据权利要求 1 所述的方法， 其特征在于， 所述催化剂在使用前 用 H2和 /或合成气进行还原处理。
8. 根据权利要求 1 所述的方法， 其特征在于， 在所述原料气中， 合 成气 /低碳酯摩尔比为 9〜1000/1，所述合成气中氢气 /一氧化碳的摩尔比为 0.06〜300/1。
9. 根据权利要求 8所述的方法， 其特征在于， 在所述原料气中， 合 成气 /低碳酯摩尔比为 40〜560/1， 所述合成气中氢气 /一氧化碳的摩尔比 0.3〜丽 1。
10. 根据权利要求 1所述的方法， 其特征在于， 所述合成气中含有二 氧化碳、 氮气和甲垸， 并且所述二氧化碳、氮气和甲垸占所述合成气的摩 尔百分含量为 3〜13%。
11. 根据权利要求 1所述的方法，其特征在于，所述反应温度为 180〜 300°C， 所述反应压力为 1.0〜10.0MPa， 所述反应体积空速为 400-30000 mlg-1^1 , 并且所述低碳酯质量空速为 0.1〜1.0h—
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