WO2010060345A1 - 一种多羟基化合物制乙二醇的方法 - Google Patents

一种多羟基化合物制乙二醇的方法 Download PDF

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WO2010060345A1
WO2010060345A1 PCT/CN2009/074821 CN2009074821W WO2010060345A1 WO 2010060345 A1 WO2010060345 A1 WO 2010060345A1 CN 2009074821 W CN2009074821 W CN 2009074821W WO 2010060345 A1 WO2010060345 A1 WO 2010060345A1
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Prior art keywords
catalyst
reaction
active component
polyhydroxy compound
ethylene glycol
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French (fr)
Inventor
张涛
郑明远
王爱琴
纪娜
庞纪峰
邰志军
周立坤
陈经广
王晓东
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to ES09828605.7T priority Critical patent/ES2507578T3/es
Priority to CA2722995A priority patent/CA2722995C/en
Priority to EP09828605.7A priority patent/EP2351725B1/en
Priority to BRPI0912077-7A priority patent/BRPI0912077B1/pt
Priority to MX2010012383A priority patent/MX2010012383A/es
Publication of WO2010060345A1 publication Critical patent/WO2010060345A1/zh
Priority to US12/916,625 priority patent/US8324433B2/en
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    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
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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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    • B01J23/85—Chromium, molybdenum or tungsten
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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
    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • 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
    • 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
    • C07C29/132—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
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J27/19—Molybdenum
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions

  • the invention relates to a process for the preparation of ethylene glycol, in particular to a reaction process in which a polyhydroxy compound is subjected to catalytic hydrogenation to ethylene glycol under hydrothermal conditions.
  • Ethylene glycol is an important energy liquid fuel and is also a very important raw material for polyester synthesis.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • ethylene glycol is mainly based on the petroleum raw material route, that is, ethylene epoxidation to obtain ethylene oxide, and then hydration to obtain ethylene glycol
  • Document 1 Cui Huaweing, domestic and international ethylene glycol production development overview, chemistry Industrial, 2007, 25, (4), 15-21.
  • Document 2 Process for preparing ethanediol by catalyzing epoxyethane hydration, Patent No. CN1463960-A; CN1204103-C].
  • the synthesis method relies on non-renewable petroleum resources, and the production process includes selective oxidation or epoxidation steps, which are technically difficult, inefficient, have many by-products, high material consumption and serious pollution.
  • US5210335 Document 5 Production New process for ethylene glycol
  • Document 6 A method for producing diols and polyols by sorbitol cleavage, CN200510008652.0 generally comprises three steps: (1) starch gelatinization, enzyme liquefaction, enzyme Glucose process to obtain glucose (2) Glucose is hydrogenated by noble metal ruthenium or nickel catalyst to obtain sorbitol (3) sorbitol hydrogenate at high temperature and high pressure to form product polyol, mainly propylene glycol, glycerol, ethylene glycol. Among them, the yield of ethylene glycol is in the range of 10-30%. The preparation process is cumbersome. The process provided by the present invention has the advantage that the reaction process is simple and the yield of ethylene glycol in the product is high. Summary of the invention
  • Polyhydroxy compounds including starch, hemicellulose, sucrose, glucose, fructose, fructan
  • the technical solution adopted by the present invention is: using a polyhydroxy compound, including starch, semi-fiber
  • the vitamins, sucrose, glucose, fructose, and fructan are the reaction materials, and the catalytic hydrogenation reaction is carried out in water in a closed high-pressure reactor.
  • the active components of the catalyst are composed of two parts, and some are transition metals of groups 8, 9 and 10.
  • One or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum; the other part is metallic molybdenum and / or tungsten, or carbides, nitrides, phosphorus with molybdenum and / or tungsten Compound.
  • the reaction is carried out in a closed high pressure reactor.
  • the initial pressure of hydrogen in the reactor at room temperature is l-12 MPa, the reaction temperature is 120-300 ° C, and the reaction time is not less than 5 minutes.
  • the preferred reaction temperature is 180-250 ° C.
  • the initial pressure of hydrogen in the reactor is preferably 3-7 MPa at room temperature, and the preferred reaction time is 30 min - 3 h.
  • the weight ratio of the second portion to the active component of the first portion is in the range of from 0.02 to 1600 times, preferably in the range of from 0.3 to 60 times by weight.
  • the active component is supported on a carrier comprising one or more complexes of activated carbon, alumina, silica, silicon carbide, zirconia, zinc oxide, titanium dioxide.
  • a carrier comprising one or more complexes of activated carbon, alumina, silica, silicon carbide, zirconia, zinc oxide, titanium dioxide.
  • the content of the second part of the active component metal on the catalyst is from 0.05 to 50% by weight, preferably from 1 to 30% by weight, preferably from 10 to 60% by weight.
  • the catalyst is an unsupported framework metal catalyst having an active component as a catalyst skeleton, such as Raney nickel.
  • the mass ratio of the polyol of the reaction raw material to water is 1:200-1:4, and the mass ratio of the polyhydroxy compound to the catalyst is 1:1 to 100:1.
  • the reaction process of the present invention is simple. Compared with the prior art polyhydroxy compound ethylene glycol technology, the present invention does not need to pre-hydrogenate the polyhydroxy compound to obtain sorbitol and then cleaves into ethylene glycol, but can realize the raw material by only one step reaction process.
  • the product ethylene glycol has a simple reaction process.
  • the reaction process has high product yield and selectivity, and the yield of ethylene glycol can reach more than 50%, which has a good application prospect.
  • Example 1 Preparation of metal tungsten catalyst: The ammonium tungstate ammonia solution (mass concentration 0.4 g/ml) was immersed on the activated carbon support, dried in an oven at 120 °C for 12 h, and then placed in a 3 ⁇ 4 atmosphere at 700 ° C for reduction for 1 h. The tungsten loading is 20 ⁇ 1% W/AC.
  • Metal nickel-tungsten catalyst preparation The tungsten catalyst prepared according to Example 1 was further impregnated with a nickel nitrate solution, dried at 120 ° C, and reduced at 400 ° C for 2 h to obtain Ni-W/AC (5 wt% Ni- 18 wt% W) Catalyst.
  • Ni/AC, Ni/Si0 2 , Pt/AC, Ru/AC The activated carbon carrier was impregnated with nickel nitrate, chloroplatinic acid and antimony trichloride aqueous solution, and dried at 120 °C for 12 h. The catalyst was reduced in a hydrogen atmosphere at 450 ° C for 1 h to obtain a catalyst of Ni/AC (5 wt% Ni), Pt/AC (0.5 wt% Pt), and Ru/AC (5 wt% Ru). The activated carbon support was replaced by Si0 2 , and the Ni/Si0 2 C15 wt% Ni) catalyst was obtained in the same manner.
  • tungsten carbide catalyst Preparation of tungsten carbide catalyst: The ammonium tungstate ammonia solution (mass concentration 0.4 g/ml) was immersed on the activated carbon support (AC), and after drying in an oven at 120 °C for 12 h, the catalyst precursor was placed in a 3 ⁇ 4 atmosphere at 800 °. C was subjected to a carbothermal reaction for 1 h to obtain a W 2 C/AC catalyst having a tungsten loading of 20 wt%.
  • AC activated carbon support
  • Ni-W 2 C /AC 5 wt %Ni- 18 wt% W
  • ruthenium tungsten carbide catalyst The mixed solution of antimony trichloride and ammonium metatungstate was immersed in an activated carbon carrier, and dried in an oven at 120 ° C for 12 h, then the catalyst precursor was placed in a H 2 atmosphere at 700 ° C for carbon heat. After reacting for 1 h, a Ru-W 2 C/AC (5 wt% Ru-10 wt% W) catalyst having a ruthenium loading of 5% and a tungsten loading of 10% was obtained.
  • Ru-W 2 C/AC 5 wt% Ru-10 wt% W
  • Cobalt nitrate and ammonium molybdate were arranged in a mixed solution according to a molybdenum/cobalt mass ratio of 2:1, and then immersed in an activated carbon carrier, and dried in an oven at 120 ° C for 12 h, then the catalyst precursor was placed.
  • the carbothermal reaction was carried out at 700 ° C for 1 h in an H 2 atmosphere to obtain a Co-Mo 2 C/AC catalyst (10 wt% Co-20 wt% Mo).
  • tungsten nitride catalyst A solution of ammonium tungstate (concentration of 0.2 g/ml) is impregnated on the activated carbon support. After drying in an oven at 120 °C for 12 h, it was nitrided at 700 °C for 1 h in an NH 3 atmosphere to obtain W 2 N/AC with a tungsten loading of 15 ⁇ ⁇ %.
  • Ni-W 2 N /AC catalyst 15 wt% Ni-15 wt% W.
  • Ni-Mo 2 N /SiO 2 catalyst 15 wt% Ni -15 wt% Mo).
  • Ni-Mo/Al 2 0 3 catalyst The mixed solution of nickel nitrate and ammonium molybdate was immersed on an alumina carrier, and after drying in an oven at 120 ° C for 12 h, the catalyst precursor was placed in a hydrogen atmosphere at 700 ° C. The reduction was carried out for 1 h to obtain a Ni-Mo/Al 2 O 3 catalyst (15 wt% Ni-15 wt% Mo).
  • molybdenum phosphide catalyst Preparation of molybdenum phosphide catalyst: Ammonium molybdate and diammonium phosphate were formulated into a solution at a ratio of molybdenum to phosphorus atomic ratio of 1:1.2. The solution was immersed in a Ti0 2 support, dried at 120 ° C, and reduced with hydrogen at 650 ° C for 2 h to obtain a MoP/Ti 2 2 catalyst (10 wt% Mo).
  • starch can be converted to ethylene glycol in high yield on various polymetallic catalysts involved in the present invention. Among them, the yield on Ni-W/AC can reach 56%.
  • the high yield of starch can be converted to ethylene glycol by combining the catalyst containing the active component of tungsten and molybdenum with the mechanical mixing of the 8,9,10 metal catalyst containing hydrogenation properties.
  • sucrose can be converted into ethylene glycol in a high yield on various polymetallic catalysts involved in the present invention.
  • High-yield conversion of sucrose to ethylene glycol can also be achieved by combining the catalyst containing the active component of tungsten and molybdenum with mechanically mixed catalysts of the 8, 9, 10 metal catalyst containing hydrogenation properties.
  • glucose can be converted into ethylene glycol in a high yield on various polymetallic catalysts involved in the present invention.
  • High-yield conversion of glucose to ethylene glycol can also be achieved by combining the catalyst containing the active component of tungsten and molybdenum with mechanical mixing of the Group 8, 9, 10 metal catalyst containing hydrogenation properties.
  • fructose can be converted into ethanol in a high yield on various catalysts involved in the present invention.
  • hemicellulose can be converted into ethylene glycol in a high yield on various catalysts involved in the present invention.
  • the yield can reach more than 50%.
  • various polyols have excellent ethylene glycol yields over a certain reaction time on a nickel-tungsten catalyst.
  • the preferred time is between 30 min and 3 h.
  • the preferred catalyst according to the present invention is a reaction result of starch and glucose as a reaction raw material (reaction condition example 16), and a patent publication: a method for producing a diol and a polyol by sorbitol cleavage, CN200510008652.0 For a comparison of the ethylene glycol yields during the reaction, see Table IX.
  • the ethylene glycol yield in the present invention is significantly higher. Moreover, the reaction process of the present invention is simpler.

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Description

一种多羟基化合物制乙二醇的方法 技术领域
本发明涉及乙二醇的制备方法， 具体地说是多羟基化合物在水热条 件下经过一歩催化加氢降解制乙二醇的反应过程。 背景技术
乙二醇是重要的能源液体燃料， 也是非常重要的聚酯合成原料， 例如， 用于聚对 苯二甲酸乙二酯（PET)， 聚萘二甲酸乙二醇酯（PEN)， 还可以用作防冻剂、润滑剂、 增塑剂、 表面活性剂等， 是用途广泛的有机化工原料。
目前， 乙二醇的工业生产主要是采用石油原料路线， 即乙烯环氧化后得到环氧乙 烷， 然后水合得到乙二醇【文献 1 : 崔小明， 国内外乙二醇生产发展概况， 化学工业， 2007， 25， (4), 15-21. 文献 2： Process for preparing ethanediol by catalyzing epoxyethane hydration, Patent No. CN1463960-A; CN1204103-C】。合成方法依赖于不可 再生的石油资源，而且生产过程中包括选择氧化或环氧化步骤，技术难度大，效率低， 副产物多， 物耗高且污染严重。
利用具有可再生性的生物质制备乙二醇， 可以减少人类对化石能源物质的依赖， 有利于实现环境友好和经济可持续发展。 多羟基化合物， 包括淀粉、 半纤维素、 葡萄 糖、 蔗糖、 果糖、 果聚糖在自然界中广泛存在。 随着农业技术的发展， 其产量日益增 长。发展以多羟基化合物制备乙二醇，不仅可以在一定程度上降低对石油资源的依赖， 同时， 有助于实现农产品深加工制高附加值化学品。 目前， 以多羟基化合物制多元醇 的技术【文献 3： Process for the preparation of lower polyhydric alcohols, patent, No. US5107018. 文献 4: Preparation of lower polyhydric alcohols, patent, No. US5210335 文献 5: —种生产乙二醇的新工艺， CN200610068869.5 文献 6: —种由山梨醇裂解 生产二元醇和多元醇的方法， CN200510008652.0】一般包括三个步骤： （1 ) 淀粉经 过糊化、 酶液化、 酶糖化过程得到葡萄糖 （2) 葡萄糖经过贵金属钌或镍催化剂加氢 得到山梨醇（3 ) 山梨醇在高温高压下氢解生成产物多元醇， 主要为丙二醇、 丙三醇、 乙二醇。 其中， 乙二醇的收率在 10-30%范围。 制备过程繁琐。 本发明提供的方法具 有反应过程简单， 而且产物中乙二醇收率高的显著优点。 发明内容
本发明的目的在于提供一种多羟基化合物制乙二醇的方法。多羟基化合物（包括 淀粉、 半纤维素、 蔗糖、 葡萄糖、 果糖、 果聚糖）经过一步催化加氢降解过程， 高收 率、 高选择性地制备乙二醇。
为实现上述目的， 本发明采取的技术方案为： 以多羟基化合物， 包括淀粉、 半纤 维素、 蔗糖、 葡萄糖、 果糖、 果聚糖为反应原料， 在密闭高压反应釜内于水中进行催 化加氢反应， 催化剂活性组分由两部分共同构成， 一部分为 8、 9、 10族过渡金属铁、 钴、 镍、 钌、 铑、 钯、 铱、 铂中的一种或几种； 另一部分为金属态的钼和 / 或钨， 或者与钼和 / 或钨的碳化物、 氮化物、 磷化物。 反应于密闭高压反应釜中进行。 反 应釜中氢气室温时的初始压力为 l-12MPa， 反应温度为 120-300°C， 反应时间不少于 5分钟。优选的反应温度为 180-250 °C，室温下反应釜中优选氢气的初始压力 3-7 MPa, 优选反应时间为 30 min - 3 h。
第二部份与第一部份的活性组分的重量比在 0.02-1600倍范围之间， 优选重量比 在 0.3-60倍范围之间。
活性组分担载在载体上， 包括活性炭、 氧化铝、 氧化硅、 碳化硅、 氧化锆、 氧化 锌、 二氧化钛一种或一种以上复合体。 第一部分活性组分金属于催化剂上的含量在
0.05-50 wt%, 优选在 1-30 wt%, 第二部分活性组分金属于催化剂上的含量为 1-80 wt%, 优选为 10-60 wt%。 或者催化剂是非负载的、 以活性组分作为催化剂骨架的骨 架金属催化剂， 例如雷尼镍等。
反应原料多羟基化合物与水的质量比为 1 :200— 1 :4， 多羟基化合物与催化剂的质 量比为 1 : 1— 100: 1。
下面所列的实施例为高压反应釜中进行， 但不排除可以通过反应器设计优化， 例 如， 采用固定床反应器、 浆态床反应器等， 实现多羟基化合物、 氢气、 以及催化剂之 间更好的传质效果， 获得更好的反应结果。
本发明具有如下优点：
1 . 以多羟基化合物包括淀粉、 半纤维素、 葡萄糖、 蔗糖、 果糖、 果聚糖为原料 制备乙二醇， 相对于现有的乙二醇工业合成路线中使用的乙烯原料， 具有原料资源可 再生的优点， 符合可持续发展的要求。
2. 多羟基化合物催化降解后， 原料分子中的碳氢氧原子得到最大程度的保留， 反应过程具有极高的原子经济性。
3. 本发明反应过程简单。 相对于已有的多羟基化合物制乙二醇技术， 本发明无 需预先对多羟基化合物进行加氢制得山梨醇后再裂解为乙二醇，而是仅仅通过一步反 应过程即可实现由原料到产物乙二醇， 反应过程简单。
4. 反应过程具有很高的产品收率和选择性， 乙二醇的收率可以达到 50%以上， 具有很好的应用前景。
下面通过具体实施例对本发明进行详细说明，但这些实施例并不对本发明的内容 构成限制。 具体实施方式
实施例 1 金属钨催化剂制备： 将偏钨酸氨溶液 （质量浓度为 0.4 g/ml) 浸渍于活性炭载体 上， 经 120 °C烘箱干燥 12 h后， 将置于 ¾气氛中 700 °C进行还原 l h， 得到钨担载 量为 20 \¥1%的 W/AC。
实施例 2
金属镍钨催化剂制备：将按照实施例 1所述制备的钨催化剂近一步浸渍硝酸镍溶 液， 经过 120 °C干燥， 400 °C还原 2 h后， 得到 Ni-W/AC (5 wt%Ni-18 wt%W) 催 化剂。
实施例 3
金属催化剂 Ni/AC, Ni/Si02, Pt/AC, Ru/AC的制备： 分别以硝酸镍、 氯铂酸、 三 氯化钌水溶液浸渍活性碳载体， 经过 120 °C 干燥 12 h后， 于 450 °C 氢气氛中还原 1 h， 分别得到催化剂 Ni/AC(5 wt%Ni), Pt/AC(0.5 wt%Pt), Ru/AC(5 wt%Ru)。 将活性碳 载体换为 Si02, 同样方法可制得 Ni/Si02C15 wt%Ni)催化剂。
实施例 4
金属铂钨催化剂制备： 将偏钨酸氨溶液 （质量浓度为 0.2 g/ml) 浸渍于氧化硅载 体上， 经 120 °C烘箱干燥 12 h后， 将置于 ¾气氛中 700 °C进行还原 l h， 得到钨担 载量为 10 Wt%的 W/Si02。 而后， 进一步浸渍氯铂酸溶液， 经 120 °C干燥， 在 350 °C 氢气还原 2 h， 得到 Pt-W/Si02 (0.5 wt%Pt- 10 wt%W) 催化剂。
实施例 5
碳化钨催化剂制备： 将偏钨酸氨溶液 （质量浓度为 0.4 g/ml) 浸渍于活性炭载体 (AC) 上， 经 120 °C烘箱干燥 12 h后， 将催化剂前体置于 ¾气氛中 800 °C进行碳 热反应 1 h， 得到钨担载量为 20 wt%的 W2C/AC催化剂。
实施例 6
镍碳化钨催化剂制备：将按照实施例 4所述制备的碳化钨催化剂近一步浸渍硝酸 镍溶液，经过 120 °C干燥， 400 °C还原 2 h后，得到 Ni-W2C /AC (5 wt%Ni- 18 wt%W) 催化剂。
实施例 7
钌碳化钨催化剂制备： 将三氯化钌与偏钨酸氨的混合溶液浸渍于活性炭载体， 经 120 °C烘箱干燥 12 h后， 将催化剂前体置于 H2气氛中 700 °C进行碳热反应 l h， 得 到钌担载量 5%， 钨担载量为 10 \^%的 Ru-W2C/AC (5 wt%Ru-10 wt%W) 催化剂。
实施例 8
钴碳化钼催化剂制备：将硝酸钴与钼酸铵按照钼 /钴质量比 2: 1配置成混合溶液， 而后浸渍于活性炭载体上， 经 120 °C烘箱干燥 12 h后， 将催化剂前体置于 H2气氛中 700 °C进行碳热反应 1 h， 得到 Co-Mo2C/AC催化剂 (10wt%Co-20wt%Mo)。
实施例 9
氮化钨催化剂制备： 偏钨酸氨溶液（质量浓度为 0.2 g/ml)浸渍于活性炭载体上， 经 120 °C烘箱干燥 12 h后， 将置于 NH3气氛中 700 °C进行氮化 1 h， 得到钨担载量 为 15 \¥〖％的 W2N/AC。
实施例 10
镍氮化钨催化剂制备： 将偏钨酸氨和硝酸镍按照钼 /镍质量比为 1 : 1的比例制成 混合溶液， 其中， 钼酸铵的质量浓度为 0.2 g/ml。 将混合溶液浸渍活性炭载体（AC)。 经 120 °C烘箱干燥 12 h后， 将催化剂前体置于 NH3气氛中 700 °C下氮化 l h， 得到 Ni-W2N /AC催化剂 （ 15 wt%Ni-15 wt% W)。
实施例 11
氮化钼催化剂制备：将钼酸铵溶液（质量浓度为 0.3 g/ml)浸渍活性炭载体（AC)。 经 120 °C烘箱干燥 12 h后， 将催化剂前体置于 NH3气氛中 700 °C下氮化 l h， 得到 Mo2N /AC催化剂 （其中 Mo 于催化剂中的担量为 25 wt%， 即 25 wt%Mo)。
实施例 12
镍氮化钼催化剂制备： 将钼酸铵和硝酸镍按照钼 /镍质量比为 1 : 1的比例制成混 合溶液，其中，钼酸铵的质量浓度为 0.27 g/ml。而后，将混合溶液浸渍二氧化硅载体。 经 120 °C烘箱干燥 12 h后， 将催化剂前体置于 NH3气氛中 700 °C下氮化 1 h ， 得到 Ni-Mo2N /Si02催化剂 （ 15 wt% Ni -15 wt% Mo )。
实施例 13
Ni-Mo/Al203催化剂制备： 将硝酸镍与钼酸铵的混合溶液浸渍于氧化铝载体上， 经过 120 °C烘箱干燥 12 h后， 将催化剂前体置于氢气氛中 700 °C下还原 1 h， 得到 Ni-Mo/Al203催化剂 （ 15 wt%Ni-15 wt%Mo)。
实施例 14
磷化钼催化剂制备： 将钼酸铵、 磷酸氢二铵按照钼磷原子比为 1:1.2的比例配成 溶液。 将溶液浸渍于 Ti02载体上， 经过 120 °C干燥后， 于 650 °C下用氢气还原 2 h， 得到 MoP/Ti02催化剂 （ 10 wt% Mo )。
实施例 15
铱磷化钼催化剂制备： 将钼酸铵、 磷酸氢二铵、 氯铱酸按照一定比例配成溶液， 其中钼磷原子比为 1:1.2， 钼铱重量比为 10:1。 将溶液浸渍 Ti02载体， 经过 120 °C干 燥后，于 650 °C下用氢气还原 2小时，得到 Ir-MoP /Ti02催化齐 [J( 1 wt% Ir-10 wt% Mo)。
实施例 16
淀粉催化转化实验： 将 1.0 g多羟基化合物， 0.3 g催化剂和 100 ml水加入到 200 ml反应釜中，通入氢气置换三次气体后，充氢气至 5 MPa,升温至 240 °C 反应 30 min。 反应结束后， 降至室温， 取离心后的上清液体， 在高效液相色谱钙型离子交换柱上进 行分离并用差示折光检测器进行检测。 产物收率中仅对目标产物乙二醇以及六元醇 (包括山梨醇、 甘露醇）进行计算， 其他液体产物包括丙二醇、 丁四醇、 乙醇、 未知 成分， 以及气体产物 （C02， CH4， C2H6等） 未计算其收率。 替换催化剂的种类， 反应条件同实施例 16。 各种催化剂上淀粉的催化转化结果
(表一）。
表一 各种催化剂上， 淀粉催化转化的结果
Figure imgf000007_0001
如表一所示，淀粉能够在本发明中所涉及的各种多金属催化剂上高收率地转化为 乙二醇。 其中， Ni-W/AC上的收率可以达到 56%。 通过将含有钨、 钼活性组分的催 化剂与对含有加氢性能的 8， 9， 10族金属催化剂以机械混合的方式进行组合使用， 同样可以实现淀粉高收率转化为乙二醇。
实施例 18
替换催化剂的种类， 反应条件同实施例 16。 各种催化剂上蔗糖的催化转化结果 表二 各种催化剂上， 蔗糖催化转化的结果
Figure imgf000008_0001
如表二所示，蔗糖能够在本发明中所涉及的各种多金属催化剂上高收率地转化为 乙二醇。 通过将含有钨、 钼活性组分的催化剂与对含有加氢性能的 8， 9， 10族金属 催化剂以机械混合的方式进行组合使用， 同样可以实现蔗糖高收率转化为乙二醇。
实施例 19
替换催化剂的种类， 反应条件同实施例 16。 各种催化剂上葡萄糖的催化转化结 果 （表三）。
表三 各种催化剂上， 葡萄糖催化转化的结果
Figure imgf000008_0002
如表三所示，葡萄糖能够在本发明中所涉及的各种多金属催化剂上高收率地转化 为乙二醇。 通过将含有钨、 钼活性组分的催化剂与对含有加氢性能的 8， 9， 10族金 属催化剂以机械混合的方式进行组合使用， 同样可以实现葡萄糖高收率转化为乙二 醇。
实施例 20
替换催化剂的种类， 反应条件同实施例 16。 各种催化剂上果糖的催化转化结果 (表四）。
表四 各种催化剂上， 果糖催化转化的结果
Figure imgf000009_0001
如表四所示， 果糖能够在本发明中所涉及的各种催化剂上高收率地转化为乙 醇。
实施例 21
替换催化剂的种类， 反应条件同实施例 16。 各种催化剂上半纤维素的催化转化 结果 （表五）。
表五 各种催化剂上， 半纤维素催化转化的结果
Figure imgf000009_0002
如表五所示， 半纤维素能够在本发明中所涉及的各种催化剂上高收率地转化为 乙二醇。 收率可以达到 50%以上。
实施例 22
反应时间的影响。 不同反应时间下 Ni-W/AC (5%Ni-25%W)催化剂上各种多羟 基化合物催化转化结果 （表六）。 除反应时间不同外， 反应条件分别同实施例 16。 表六 不同反应时间下 Ni-W/AC催化剂上各种多羟基化合物催化转化结果
Figure imgf000010_0001
从表中可以看出，各种多羟基化合物在镍钨催化剂上一定的反应时间内均有优良 的乙二醇收率。 较佳时间为在 30 min -3 h。
实施例 23
反应温度的影响。 不同反应温度下 Ni-W/AC (5%Ni-25%W) 催化剂上各种多羟 基化合物催化转化结果， 见表七。 除反应温度不同外， 反应条件分别同实施例 16。
表七 不同反应温度下 Ni-W/AC催化剂上各种多羟基化合物催化转化结果
Figure imgf000010_0002
从表中可以看出，各种多羟基化合物在镍钨催化剂上一定的反应温度内均有优良 的乙二醇收率， 较佳温度在 180-250 °C附近。
实施例 24
反应压力的影响。 不同氢气压力下 Ni-W/AC (5%Ni-25%W) 催化剂上多羟基化 合物催化转化的结果， 见表八。 除反应中的氢气压力不同外， 反应条件分别同实施例 16。 表八 不同氢气压力下 Ni-W/AC催化剂上各种多羟基化合物催化转化结果
Figure imgf000011_0001
从表中可以看出，各种多羟基化合物在镍钨催化剂上一定的氢气压力下均有优良 的乙二醇收率。 较佳反应压力为 3-7 MPa。
实施例 25
本发明所涉及的较佳催化剂以淀粉、葡萄糖为反应原料的反应结果（反应条件实 施例 16 )， 与公开专利： 一种由山梨醇裂解生产二元醇和多元醇的方法， CN200510008652.0所涉及的反应过程中的乙二醇收率的比较， 见表九。
表九 本发明与公开专利结果对比
Figure imgf000011_0002
显然， 本发明中的乙二醇收率明显更高。 而且， 本发明的反应过程更为简单。

Claims

权 利 要 求 书
1 . 一种多羟基化合物制乙二醇的方法， 其特征在于： 其以多羟基化合物为反应 原料， 在密闭高压反应釜内于水中进行催化加氢反应，所采用的催化剂活性组分由二 部份共同构成， 第一部份为第 8、 9、 10族的过渡金属铁、 钴、 镍、 钌、 铑、 钯、 铱、 铂中的一种或一种以上，第二部份为金属态的钼和 I或钨、或者钼和 /或钨的碳化物、 氮化物、磷化物中的一种或一种以上； 于反应釜搅拌反应； 反应釜中氢气室温时的初 始压力为 l-12MPa， 反应温度为 120-300°C， 反应时间不少于 5分钟；
第二部份与第一部份的活性组分的重量比在 0.02-1600倍范围之间。
2. 按照权利要求 1所述的方法， 其特征在于： 所述催化剂为负载型催化剂， 活 性组分担载在载体上， 所述载体为活性炭、 氧化铝、 氧化硅、 碳化硅、 氧化锆、 氧化 锌、二氧化钛一种或一种以上的复合载体； 第一部分活性组分金属于催化剂上的含量 在 0.05-50 wt%， 第二部分活性组分金属于催化剂上的含量为 1-80 wt%。
3. 按照权利要求 2所述的方法， 其特征在于： 所述第一部分活性组分金属于催 化剂上的含量优选在 1-30 wt%， 第二部分活性组分金属于催化剂上的含量优选为
10-60 wt%。
4. 按照权利要求 1所述的方法， 其特征在于： 所述催化剂也可以是非负载的、 以活性组分作为催化剂骨架的骨架金属催化剂。
5. 按照权利要求 1所述的方法， 其特征在于： 反应原料多羟基化合物与水的质 量比为 1 :200—1 :4， 多羟基化合物与催化剂的质量比为 1 : 1— 100: 1。
6. 按照权利要求 1所述的方法， 其特征在于： 优选的反应温度为 180-250 °C， 室温下反应釜中优选氢气的初始压力 3-7 MPa， 优选反应时间为 30 min - 3 h。
7. 按照权利要求 1所述的方法， 其特征在于： 所述第二部份与第一部份的活性 组分的优选重量比在 0.3-60倍范围之间。
8. 按照权利要求 1所述的方法， 其特征在于： 所述多羟基化合物为淀粉、 半纤 维素、 蔗糖、 葡萄糖、 果糖、 果聚糖中的一种或一种以上。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8222463B2 (en) 2011-07-28 2012-07-17 Uop Llc Process for generation of polyols from saccharide containing feedstock
US8222465B2 (en) 2011-07-28 2012-07-17 Uop Llc Catalytic process for continuously generating polyols
US8222462B2 (en) 2011-07-28 2012-07-17 Uop Llc Process for generation of polyols from saccharides
US8222464B2 (en) 2011-07-28 2012-07-17 Uop Llc Catalytic process for continuously generating polyols
US8323937B2 (en) 2011-07-28 2012-12-04 Uop Llc Continuous catalytic generation of polyols from cellulose
US8410319B2 (en) 2011-07-28 2013-04-02 Uop Llc Continuous catalytic generation of polyols from cellulose with recycle

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN117861676B (zh) 2022-10-10 2025-07-01 中国石油化工股份有限公司 双催化中心催化剂及其制备方法和应用和二元醇的制备方法
CN116139880B (zh) * 2023-02-24 2024-10-25 广东工业大学 一种抗硫中毒的催化燃烧用催化剂及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683293A (zh) * 2005-03-01 2005-10-19 大成多元醇投资有限公司 一种由山梨醇裂解生产二元醇和多元醇的方法
CN1919814A (zh) * 2006-09-14 2007-02-28 山东西王糖业有限公司 一种生产乙二醇的新工艺

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3928285A1 (de) * 1989-08-26 1991-02-28 Basf Ag Verfahren zur herstellung niederer, mehrwertiger alkohole
CN101723802B (zh) * 2008-10-24 2013-06-19 中国科学院大连化学物理研究所 一种纤维素制乙二醇的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683293A (zh) * 2005-03-01 2005-10-19 大成多元醇投资有限公司 一种由山梨醇裂解生产二元醇和多元醇的方法
CN1919814A (zh) * 2006-09-14 2007-02-28 山东西王糖业有限公司 一种生产乙二醇的新工艺

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2351725A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8222463B2 (en) 2011-07-28 2012-07-17 Uop Llc Process for generation of polyols from saccharide containing feedstock
US8222465B2 (en) 2011-07-28 2012-07-17 Uop Llc Catalytic process for continuously generating polyols
US8222462B2 (en) 2011-07-28 2012-07-17 Uop Llc Process for generation of polyols from saccharides
US8222464B2 (en) 2011-07-28 2012-07-17 Uop Llc Catalytic process for continuously generating polyols
US8323937B2 (en) 2011-07-28 2012-12-04 Uop Llc Continuous catalytic generation of polyols from cellulose
US8410319B2 (en) 2011-07-28 2013-04-02 Uop Llc Continuous catalytic generation of polyols from cellulose with recycle

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