CN106987285A - Multiphase preparation method of higher monohydric alcohol biofuel - Google Patents

Multiphase preparation method of higher monohydric alcohol biofuel Download PDF

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CN106987285A
CN106987285A CN201710166309.1A CN201710166309A CN106987285A CN 106987285 A CN106987285 A CN 106987285A CN 201710166309 A CN201710166309 A CN 201710166309A CN 106987285 A CN106987285 A CN 106987285A
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bed reactor
hydrogen
fixed bed
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CN106987285B (en
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王铁军
马隆龙
仇松柏
翁育靖
陈伦刚
孙飞
王晨光
张琦
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中国科学院广州能源研究所
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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
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic compounds
    • C10L2200/0461Fractions defined by their origin
    • C10L2200/0469Renewables or materials of biological origin
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/12Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel

Abstract

The invention discloses a multiphase preparation method of higher monohydric alcohol biofuel, comprising: allowing sugar alcohol solution having a concentration of 5-30% by weight and hydrogen to flow into a fixed-bed reactor in concurrent flow manner, and subjecting the sugar alcohol in multiphase state to selective deoxidation under the temperature of 140-300 DEG C, hydrogen pressure of 2-10 MPa and liquid space velocity of 1.0-10.0 h<-1> through the synergy of Ru-MoOx/Ac or Ru-MoOx/CNT multifunctional catalyst so as to prepare the higher monohydric alcohol biofuel using amyl alcohol and hexyl alcohol as main components; sugar alcohol conversion rate is up to 99%; the selectivity of higher monohydric alcohol in the biofuel is up to 80% and above; the method has the advantages of good process simplicity, greenness, low carbon, good mildness of conversion conditions, low hydrogen consumption, high energy utilization rate, high added value of products and the like, and facilitates industrial production, and both the obtained amyl alcohol and hexyl alcohol are important chemical materials, solvents and additives.

Description

一种多相态制备高级一元醇生物燃料的方法 A multi-phase state higher monohydric alcohol preparation method biofuel

技术领域: FIELD:

[0001] 本发明涉及低碳生物燃料技术领域,具体涉及一种多相态制备高级一元醇生物燃料的方法。 [0001] The present invention relates to low-carbon biofuels technologies, and particularly relates to a multiphase preparing higher monohydric alcohol biofuel method.

背景技术: Background technique:

[0002] 生物质是可再生能源中唯一可以生产液体燃料和化学品的碳资源。 [0002] Biomass is a renewable carbon resources can be produced only liquid fuels and chemicals. 农林废弃物等木质纤维素类生物质资源十分丰富,通过气化合成技术可以将其转化为醇、醚及烃等多种产品,但气化费托合成技术得到的产物碳链分布宽,生产的粗油还需蒸馏切割分离不同馏分,技术路线较长,小规模下难有经济性。 Agricultural and forestry waste and other lignocellulosic biomass is rich in resources, which can be converted to alcohols, ethers and other products by gasification of hydrocarbon synthesis techniques, but the distribution of carbon chain gasification product Fischer-Tropsch synthesis technology is wide, the production of crude oil distillation cut the need to separate the different fractions, a long line technology, small scale difficult economy. 木质纤维素经水解发酵可生产燃料乙醇,但乙醇发酵菌种还未能实现五碳糖的高效转化,乙醇蒸馏提纯的能耗居高不下,目前纤维素燃料乙醇的成本还较高,车用乙醇汽油因其需要防水、防腐蚀等原因,在调和、储运、销售及售后服务等方面增加了成本。 Hydrolysed lignocellulosic fermentation to produce fuel ethanol, but ethanol Fermentation also failed to achieve efficient conversion of pentose, ethanol distillative purification of high energy consumption, the current cost of fuel ethanol cellulosic also higher, vehicle ethanol gasoline needs because of its waterproof, anti-corrosion and other reasons, increasing the cost in terms of reconciliation, storage and transportation, sales and after-sales service. 乙醇汽油易吸水、热值较低、燃用乙醇汽油的汽车动力不足等问题,阻碍了乙醇汽油的应用,前景不容乐观。 Ethanol gasoline easy to absorb water, low calorific value, lack of vehicle power fueled with ethanol, gasoline and other issues that hinder the use of ethanol gasoline, the outlook is not optimistic. 因此,探索一种新的生物质高效转化为生物液体燃料途径是国内外研宄热点之一。 Therefore, to explore a new biomass into bio-liquid fuel efficient route is one of a Subsidiary hotspots at home and abroad.

[0003] 近年来,生物质通过水解和加氢手段获取糖醇,再通过催化加氢、水相重整技术可以合成氢气、液体烷烃及化学品。 [0003] In recent years, the biomass obtained by means of hydrolysis and hydrogenation of a sugar alcohol, and then by catalytic hydrogenation, reforming the aqueous phase synthesis techniques may be hydrogen, alkanes and liquid chemicals. Huber等人(Angew Chem Int Ed,2004,43:1549)制备了一种Pt/Al2〇3-Si02催化剂,可以有效地控制山梨醇水相重整选择性合成Cl〜C6烷烃,在225 °C,3 • 96MPa下,烧烃的总选择性可以达到58〜89 %,其中正戊烷和正己烷的选择性分别为21%和40%。 Huber et al. (Angew Chem Int Ed, 2004,43: 1549) one kind of Pt / Al2〇3-Si02 catalyst was prepared, and can effectively control the selective synthesis of sorbitol aqueous phase reforming Cl~C6 alkane, at 225 ° C , the 3 • 96MPa, burning hydrocarbons 58~89% overall selectivity can be achieved, wherein the selectivity of n-pentane and n-hexane is 21% and 40%, respectively. 中国专利CN 10155035〇A公开了一种生物汽油的制备方法及催化剂制备工艺, 其特点在于以山梨醇为原料,采用负载型贵金属Pt/HZSM-5催化剂,利用微型浆态床进行高压加氢反应,可以较高选择性地得到液体烷烃产品。 Chinese Patent CN 10155035〇A discloses a method for preparing a biological catalyst preparation process and gasoline, characterized in that sorbitol as raw materials, supported noble metal Pt / HZSM-5 catalyst, slurry bed using a micro high pressure hydrogenation reaction , higher selectivity can be obtained the liquid paraffin product. 但生物质水相催化转化为烷烃需要将糖醇分子中的氧原子全部脱除,该过程不仅氢气消耗量大,而且糖醇转化为烷烃的质量收率较低,该过程转化温度较高、能耗较大,整体效率仍有待提高。 However, the catalytic conversion of biomass the aqueous phase needs to be an oxygen atom alkanes sugar alcohol molecule all removed, the hydrogen consumption of the process is not only large, but also the quality of the sugar alcohol yield of conversion of alkane is low, the higher temperature conversion process, large energy consumption, overall efficiency is still to be improved.

发明内容: SUMMARY:

[0004] 本发明的目的是提供一种多相态制备高级一元醇生物燃料的方法,在相对较低的转化温度下,选择性脱除糖醇分子中的氧原子,定向制取以戊醇和己醇为主要组分的高级一元醇生物燃料,具有转化条件温和、氢气消耗低、能源利用效率高及产物附加值高等优点。 [0004] The object of the present invention is to provide a multiphase preparing higher monohydric alcohol biofuel methods, at relatively low conversion temperatures, selective removal of the oxygen atom in the molecule a sugar alcohol, amyl alcohol and directed to the preparation of hexanol higher monohydric alcohols biofuel a main component, having a mild conversion conditions, low hydrogen consumption, energy efficiency and high value-added products advantages.

[0005] 本发明是通过以下技术方案予以实现的: [0005] The present invention is to be implemented by the following technical scheme:

[0006] —种多相态制备高级一元醇生物燃料的方法,该方法将浓度为5-30wt %的糖醇水溶液与氢气并流进入固定床反应器,在温度为140-3〇(TC、氢气压力为2_10MPa和液体空速为1 • 0-10 • 01T1的条件下,在Ru-MoOx/AC或Ru-M〇0x/CNT多功能催化剂协同作用下,糖醇在多相态的状态下选择性脱氧制备以戊醇和己醇为主要组分的高级一元醇生物燃料;所述糖醇水溶液为淀粉类和木质纤维素类生物质的水解糖液(主要成分为葡萄糖和木糖)或水解糖液加氢后的多元醇(主要成分为山梨醇和木糖醇)水溶液;该方法包括以下步骤: [0006] - Preparation of higher monohydric alcohols method multiphase kinds of biofuels, which a concentration of 5-30wt% aqueous solution of sugar alcohol and hydrogen flow into the fixed bed reactor at a temperature of 140-3〇 (the TC, hydrogen pressure and LHSV 2_10MPa 1 • 0-10 • 01T1 conditions in Ru-MoOx / AC or Ru-catalyst synergistic multifunctional CNT M〇0x / sugar alcohol in the multiphase state High-deoxy-selective preparation of biofuels monoalcohol pentanol and hexanol as a main component; the sugar alcohol aqueous solution of starch and sugar hydrolyzing lignocellulosic biomass (mainly composed of glucose and xylose) or hydrolysis after hydrogenation polyol sugar (mainly composed of xylitol and sorbitol) solution; the method comprising the steps of:

[0007] 1)将Ru-M〇〇X/AC或Ru-MoOx/CNT多功能催化剂装填于固定床反应器的反应管恒温区,室温下置换氢气直至固定床反应器内空气被氢气置换完全; [0007] 1) Ru-M〇〇X / AC or Ru-MoOx / CNT multifunctional catalyst packed in a reaction tube of a fixed bed reactor temperature zone, fixed bed reactor hydrogen was replaced until the air is replaced with hydrogen at room temperature for completely ;

[0008] 2)通入氢气,同时固定床反应器以5°C/min的升温速率从常温升至350°C并于350 °C恒温3-5小时直至Ru-MoOx/AC或Ru-MoOx/CNT多功能催化剂充分还原; [0008] 2) introducing hydrogen, while the fixed bed reactor at a heating rate of 5 ° C / min was raised to 350 ° C from room temperature and at 350 ° C for 3-5 hours until the Ru-MoOx / AC or Ru-MoOx / CNT multifunctional catalyst sufficiently reduced;

[0009] 3)将固定床反应器温度降至设定的反应温度140-300°C,将浓度为5-30wt%糖醇水溶液与氢气按体积流量比1:50-1: 200并流进入固定床反应器,控制液体空速为1.0-10.Oh1和氢气压力2-10MPa,使糖醇水溶液在固定床反应器内发生蒸发-冷凝反复交替的多相态下在Ru-Mo0x/AC或Ru-MoOx/CNT催化剂表面选择性脱氧反应转化为戊醇和己醇; [0009] 3) The reaction temperature of a fixed bed reactor temperature was lowered to set 140-300 ° C, a concentration of 5-30wt% aqueous solution of a sugar alcohol with hydrogen by volume flow ratio of 1: 50-1: 200 and flow into fixed bed reactor, the control LHSV and a hydrogen pressure of 2 to 10 MPa 1.0-10.Oh1, sugar alcohol solution evaporation occurs in a fixed bed reactor - the Ru-Mo0x / AC condensed or alternately repeated multiphase ru-MoOx / CNT selective deoxygenation catalyst surface into pentanol and hexanol;

[0010] 4)从固定床反应器出口排出的气液混合物经2-10MPa高压冷凝,分离为液体产物和不凝性气体产物,液体产物分层为油相和水相,油相为戊醇和己醇的混合物;水相用于水解工艺制备水解糖醇液,气相主要为未参与反应的过量氢气,经循环压缩机增压后再次进入固定床反应器循环利用。 [0010] 4) a gas-liquid mixture discharged from the outlet of the fixed bed reactor via a high pressure 2-10MPa condensed, separated into a liquid product and non-condensable gas product, the liquid product was stratified into oil and water phases, the oil phase of amyl alcohol hexanol mixture; the aqueous phase hydrolysis process for the preparation of an excess of hydrogen was hydrolyzed sugar alcohols, mainly the unreacted gas, and after entering the fixed bed reactor pressurized recycle compressor again recycled.

[0011] 步骤1)室温下置换氢气直至固定床反应器内空气被氢气置换完全的具体步骤如下:在室温下通入氢气进入固定床反应器中至反应器总压达到0.3MPa停止加入氢气,静置1-10分钟后固定床反应器排气至常压,如此反复直至固定床反应器内空气被氢气置换完全。 [0011] Step 1) substitution of hydrogen at room temperature until the air is completely replaced with the particular step of a fixed bed reactor hydrogen as follows: hydrogen gas at room temperature through a fixed bed reactor into the reactor to a total pressure of 0.3MPa hydrogen feed is discontinued, after standing for 1 to 10 minutes fixed bed reactor was vented to atmospheric pressure, and so forth until the air within the fixed bed reactor is fully replaced with hydrogen.

[0012] 所述Ru-Mo0x/AC催化剂的制备方法如下:椰壳活性炭采用硝酸浸泡12小时,而后采用去离子水清洗,反复浸泡和清洗3次,充分除去椰壳活性炭中的盐分;而后在处理后的椰壳活性炭上负载30wt %Mo02,干燥后二次负载3wt % Ru,制备出Ru-Mo0x/AC催化剂。 [0012] The preparation of Ru-Mo0x / AC catalyst was as follows: coconut shell activated carbon using nitrate soak 12 hours and then washed with deionized water, and washed three times by repeated dipping, in fully desalted coconut shell activated carbon; and then in the 30wt% Mo02 supported on coconut shell activated carbon treated, and dried secondary load 3wt% Ru, to prepare a Ru-Mo0x / AC catalyst. _3] 所述Ru—Mo0x/CNT催化剂的制备方法如下:多壁碳纳米管采用硝酸浸泡12小时,而后采用去离子水清洗,反复浸泡和清洗3次,充分除去多壁碳纳米管中的金属组分;而后在处理后多壁碳纳米管上负载30wt%M〇02,干燥后二次负载2wt%Ru,制备出Ru-MoOx/CNT催化剂。 _3] The Ru-Mo0x / CNT catalyst prepared as follows: Multi-walled carbon nanotubes using nitric acid soak 12 hours and then washed with deionized water, soaking and washed repeatedly three times to sufficiently remove the metal MWNTs component; M〇02 then loaded in 30wt% MWNTs after treatment, after drying the second load 2wt% Ru, to prepare a Ru-MoOx / CNT catalyst.

[0014] 本发明的有益效果如下:本发明在相对较低的转化温度下,选择性脱除糖醇分子中的氧原子,定向制取以戊醇和己醇为主要组分的高级一元醇生物燃料,糖醇转化率达99%,生物燃料中高级一元醇选择性达80%以上,具有过程简单、绿色低碳、转化条件温和、 氢气消耗低、能源利用效率高及产物附加值高等优点,易于工业化生产,得到的戊醇和己醇均是重要的化工原料、溶剂及添加剂,可广泛用于有机合成、涂料、精细化工添加剂等,亦可高比例加入到车用汽油和柴油中,与乙醇汽油相比,在防水、腐蚀、热值及发动机动力等方面均具有明显优势,适用于所有普通商用汽柴油车辆及船舶上的动力设备。 [0014] Advantageous effects of the present invention are as follows: the present invention at relatively low conversion temperatures, selective removal of the oxygen atom of a sugar alcohol molecules, the orientation of advanced preparing monohydric alcohol in biological pentanol and hexanol as a main component fuel, 99% conversion of a sugar alcohol, a monohydric alcohol biofuel senior selectivity of 80% or more, having a simple process, mild green and low conversion conditions, low hydrogen consumption, energy efficiency and high value-added products advantages, industrial production easy, pentanol and hexanol obtained are important chemical raw materials, solvents and additives can be widely used in organic synthesis, coatings, fine chemicals and other additives can also be added to the high proportion of gasoline and diesel, ethanol compared to gasoline, in terms of waterproofing, corrosion, and other calorific value and the engine power has obvious advantages for power equipment on all ordinary commercial gasoline and diesel vehicles and ships.

具体实施方式: Detailed ways:

[0015] 以下是对本发明的进一步说明,而不是对本发明的限制。 [0015] The following is a further explanation of the invention, not limitation of the invention.

[0016] 实施例1: [0016] Example 1:

[0017]椰壳活性炭采用硝酸浸泡I2小时,而后采用去离子水清洗,反复浸泡和清洗3次, 充分除去椰壳活性炭中的盐分。 [0017] Coconut shell activated carbon using nitrate immersion I2 hours, then washed with deionized water, soaking and repeatedly washed three times, sufficiently desalted coconut shell activated carbon. 而后在处理后的椰壳活性炭上负载3〇wt%Mo02,干燥后二次负载3wt %Ru,制备出Ru_Mo0x/AC催化剂。 Then 3〇wt% Mo02 supported on coconut shell activated carbon treated, and dried secondary load 3wt% Ru, prepared Ru_Mo0x / AC catalyst.

[0018] 将3〇Og多功能催化剂Ru-Mo0x/AC装填于固定床反应器的反应管恒温区,在室温下通入氢气进入固定床反应器中,至反应器总压达到0.3MPa停止加入氢气,静置丨-⑺分钟后固定床反应器排气至常压,如此反复充气排气3-5次,直至固定床反应器内空气被氢气置换完全; [0018] The multifunctional catalyst 3〇Og Ru-Mo0x / AC filled into a reaction tube of a fixed bed reactor temperature zone, into hydrogen gas at room temperature into the fixed bed reactor, the reactor to a total pressure of 0.3MPa was stopped hydrogen, Shu -⑺ minutes after standing a fixed bed reactor vented to atmospheric pressure, and so forth 3-5 times a pneumatic exhaust, a fixed bed reactor until the air is completely replaced with hydrogen;

[0019] 向固定床反应器中持续通入氢气,同时固定床反应器以5 °C/min的升温速率从常温升至350°C并于350°C恒温5小时,直至催化剂充分还原; [0019] with hydrogen to a fixed bed reactor continuously on while the fixed bed reactor at a heating rate of 5 ° C / min from normal temperature was raised to 350 ° C and 350 ° C in a thermostat for 5 hours until the catalyst is sufficiently reduced;

[0020] 将固定床反应器温度降至反应温度300°C,浓度为2〇wt%糖醇水溶液与氢气按体积流量比1: 50并流进入固定床反应器,严格控制液体空速1 • S1T1和氢气压力恒定在8.5-8.7MPa进行糖醇在多相态下选择性脱氧反应; [0020] The fixed bed reactor temperature was lowered to the reaction temperature of 300 ° C, a sugar alcohol concentration 2〇wt% by volume aqueous solution of hydrogen flow rate ratio of 1:50 and flow into a fixed bed reactor, the liquid space velocity of 1 • strict control and a constant hydrogen pressure for S1T1 sugar alcohol under selective deoxygenation multiphase reaction 8.5-8.7MPa;

[0021] 从固定床反应器出口排出的产物经8 .〇MPa高压冷凝后,分离为液体产物和不凝性气体产物,液体产物分层为油相和水相,油相为戊醇和己醇的混合物,选择性达82.5%。 [0021] After 8 .〇MPa high pressure condensation product is discharged from the outlet of the fixed bed reactor, and the product is separated into a liquid non-condensable gaseous product, liquid product stratified into oil and water phases, the oil phase is pentanol and hexanol mixture, selectivity of 82.5%. 水相用于水解工艺制备水解糖醇液,气相主要为未参与反应的过量氢气,经循环压缩机增压后再次进入固定床反应器循环利用。 Hydrolysis of the aqueous phase used to prepare the hydrolyzed sugar alcohol solution, excess hydrogen gas is mainly the unreacted, recycle compressor after entering the fixed bed reactor pressurized recycled again. 从气液分离器底部收集高级一元醇生物燃料,剩余的氢气经气液分离器顶部排出,经循环压缩机增压后再次进入固定床反应器循环利用。 Collected from the bottom of the gas-liquid separator higher monohydric alcohols biofuels, remaining hydrogen is discharged via the top of the gas-liquid separator, the compressor through the circulation into the fixed bed reactor pressurized recycled again.

[0022] 实施例2: [0022] Example 2:

[0023] 椰壳活性炭采用硝酸浸泡12小时,而后采用去离子水清洗,反复浸泡和清洗3次, 充分除去椰壳活性炭中的盐分。 [0023] Coconut shell activated carbon using nitrate soak 12 hours and then washed with deionized water, soaking and repeatedly washed three times, sufficiently desalted coconut shell activated carbon. 而后在处理后的椰壳活性炭上负载3〇wt%Mo〇2,干燥后二次负载3wt % Ru,制备出Ru-MoOx/AC催化剂。 Then 3〇wt% Mo〇2 load on coconut shell activated carbon treated, and dried secondary load 3wt% Ru, to prepare a Ru-MoOx / AC catalyst.

[0024] 将300g多功能催化剂Ru-MoOx/AC装填于固定床反应器的反应管恒温区,在室温下通入氢气进入固定床反应器中,至反应器总压达到〇• 3MPa停止加入氢气,静置1-10分钟后固定床反应器排气至常压,如此反复充气排气3-5次,直至固定床反应器内空气被氢气置换兀生; [0024] 300g of multifunctional catalyst Ru-MoOx / AC filled into a reaction tube of a fixed bed reactor temperature zone, into hydrogen gas at room temperature into the fixed bed reactor, the reactor to a total pressure of hydrogen gas was stopped square • 3MPa after standing for 1-10 minutes fixed bed reactor was vented to atmospheric pressure, and so forth pneumatic exhaust 3-5 times until the fixed bed reactor is purged with hydrogen and air born Wu;

[0025]向固定床反应器中持续通入氢气,同时固定床反应器以5°C/min的升温速率从常温升至350°C并于350°C恒温5小时,直至催化剂充分还原; [0025] with hydrogen to a fixed bed reactor continuously on while the fixed bed reactor at a heating rate of 5 ° C / min from normal temperature was raised to 350 ° C and 350 ° C in a thermostat for 5 hours until the catalyst is sufficiently reduced;

[0026] 将固定床反应器温度降至反应温度240 °C,浓度为15wt%糖醇水溶液与氢气按体积流量比1:100并流进入固定床反应器,严格控制液体空速1.51T1和氢气压力恒定在3.4-3.6MPa进行糖醇在多相态下选择性脱氧反应; [0026] The fixed bed reactor temperature was lowered to the reaction temperature of 240 ° C, a sugar alcohol at a concentration of 15wt% aqueous solution of hydrogen by volume flow ratio of 1: 100 and flow into a fixed bed reactor, and strictly controlling the liquid space velocity of hydrogen 1.51T1 multiphase constant pressure for selective deoxygenation sugar alcohol in 3.4-3.6MPa;

[0027] 从固定床反应器出口排出的产物经3. OMPa高压冷凝后,分离为液体产物和不凝性气体产物,液体产物分层为油相和水相,油相为戊醇和己醇的混合物,选择性达86.8%。 [0027] The product discharged from the outlet after a fixed bed reactor 3. OMPa high pressure condensed liquid product and separating non-condensable gas product, the liquid product was stratified into oil and water phases, the oil phase is pentanol and hexanol The mixture selectivity of 86.8%. 水相用于水解工艺制备水解糖醇液,气相主要为未参与反应的过量氢气,经循环压缩机增压后再次进入固定床反应器循环利用。 Hydrolysis of the aqueous phase used to prepare the hydrolyzed sugar alcohol solution, excess hydrogen gas is mainly the unreacted, recycle compressor after entering the fixed bed reactor pressurized recycled again. 从气液分离器底部收集高级一元醇生物燃料,剩余的氢气经气液分离器顶部排出,经循环压缩机增压后再次进入固定床反应器循环利用。 Collected from the bottom of the gas-liquid separator higher monohydric alcohols biofuels, remaining hydrogen is discharged via the top of the gas-liquid separator, the compressor through the circulation into the fixed bed reactor pressurized recycled again.

[0028] 实施例3: [0028] Example 3:

[0029] 多壁碳纳米管采用硝酸浸泡12小时,而后采用去离子水清洗,反复浸泡和清洗3 次,充分除去多壁碳纳米管中的金属组分。 [0029] MWNTs using nitric acid soak for 12 hours and then washed with deionized water, soaking and washed repeatedly three times to sufficiently remove the metal components of the multi-walled carbon nanotubes. 而后在处理后多壁碳纳米管上负载30wt%M〇02, 干燥后二次负载2wt % Ru,制备出Ru-Mo0x/CNT催化剂。 Then the load on M〇02 30wt% MWNTs after treatment, after drying the second load 2wt% Ru, to prepare a Ru-Mo0x / CNT catalyst.

[0030] 将300g多功能催化剂Ru-M〇0x/CNT装填于固定床反应器的反应管恒温区,在室温下通入氢气进入固定床反应器中,至反应器总压达到〇• 3MPa停止加入氢气,静置1-10分钟后固定床反应器排气至常压,如此反复充气排气3-5次,直至固定床反应器内空气被氢气置换完全; [0030] The multifunctional catalyst Ru-M〇0x 300g / CNT filled into a fixed bed reactor, the reaction tube temperature zone, into hydrogen gas at room temperature into the fixed bed reactor to a total pressure of the reactor stopped square • 3MPa after addition of hydrogen gas, allowed to stand for 1-10 minutes fixed bed reactor was vented to atmospheric pressure, and so forth 3-5 times a pneumatic exhaust, a fixed bed reactor until the air is completely replaced with hydrogen;

[0031] 向固定床反应器中持续通入氢气,同时固定床反应器以5°C/min的升温速率从常温升至350°C并于350°C恒温5小时,直至催化剂充分还原; > —一A [0031] Length of the hydrogen feed to the fixed bed reactor, a fixed bed reactor while a ramp rate of 5 ° C / min from normal temperature was raised to 350 ° C and 350 ° C in a thermostat for 5 hours until the catalyst is fully reduced;> - a a

[0032]将固定床反应器温度降至反应温度22(TC,浓度为2〇wt%糖醇水溶液与氢气按^ 积流量比1: 1〇〇并流进入固定床反应器,保持液体空速6. Oh-1和压力恒定在2 • 3-2 • 5MPa进行糖醇在多相态下选择性脱氧反应; [0032] The fixed bed reactor temperature was lowered to the reaction temperature 22 (TC, sugar alcohol concentration 2〇wt% aqueous solution of hydrogen by volume flow ratio of 1 ^: 1〇〇 and flow into a fixed bed reactor, maintained LHSV 6. Oh-1 and constant pressure for 2 • 3-2 • 5MPa sugar alcohol under selective deoxygenation multiphase reaction;

[0033]从固定床反应器出口排出的产物经2 • OMPa高压冷凝后,分离为液体产物和不凝性气体产物,液体产物分层为油相和水相,油相为戊醇和己醇的混合物,选择性达81.7%。 [0033] After 2 • OMPa high pressure condensation product is discharged from the outlet of the fixed bed reactor, and the product is separated into a liquid non-condensable gaseous product, liquid product stratified into oil and water phases, the oil phase is pentanol and hexanol The mixture selectivity of 81.7%. 水相用于水解工艺制备水解糖醇液,气相主要为未参与反应的过量氢气,经循环压缩机增压后再次进入固定床反应器循环利用。 Hydrolysis of the aqueous phase used to prepare the hydrolyzed sugar alcohol solution, excess hydrogen gas is mainly the unreacted, recycle compressor after entering the fixed bed reactor pressurized recycled again. 从气液分离器底部收集高级一元醇生物燃料,剩余的氢气经气液分离器顶部排出,经循环压缩机增压后再次进入固定床反应器循环利用。 Collected from the bottom of the gas-liquid separator higher monohydric alcohols biofuels, remaining hydrogen is discharged via the top of the gas-liquid separator, the compressor through the circulation into the fixed bed reactor pressurized recycled again.

Claims (3)

1.一种多相态制备高级一元醇生物燃料的方法,其特征在于,该方法将浓度为5-3〇wt %的糖醇水溶液与氢气并流进入固定床反应器,在温度为140-300°C、氢气压力为2-lOMPa和液体空速为1.0-10.0h_1的条件下,在Ru-MoOx/AC或Ru-MoOx/CNT多功能催化剂协同作用下,糖醇在多相态的状态下选择性脱氧制备以戊醇和己醇为主要组分的高级一元醇生物燃料;所述糖醇水溶液为淀粉类和木质纤维素类生物质的水解糖液或水解糖液加氢后的多元醇水溶液;该方法包括以下步骤: 1) 将Ru-M〇0x/AC或Ru-MoOx/CNT多功能催化剂装填于固定床反应器的反应管恒温区, 室温下置换氢气直至固定床反应器内空气被氢气置换完全; 2) 通入氢气,同时固定床反应器以5tVmin的升温速率从常温升至35(TC并于350°C恒温3-5小时直至Ru-M〇0x/AC或Ru-MoOx/CNT多功能催化剂充分还原; 3) 将固定床反应器温度降至设定的 A multiphase preparing higher monohydric alcohol biofuels, characterized in that the method 5-3〇wt% concentration of aqueous solution of sugar alcohol and hydrogen flow into the fixed bed reactor at a temperature of 140- 300 ° C, a hydrogen pressure of 2-lOMPa conditions and LHSV 1.0-10.0h_1, in Ru-MoOx / AC or Ru-MoOx CNT synergistic multifunctional catalyst / sugar alcohol multiphase state in preparation of higher monohydric alcohols biofuels pentanol and hexanol as a main component selective deoxygenation; after hydrolysis of the sugar alcohol aqueous sugar or sugar hydrolyzed starch and lignocellulosic biomass hydrogenation polyol water; the method comprising the steps of: 1) Ru-M〇0x / AC or Ru-MoOx / CNT multifunctional catalyst packed in a reaction tube fixed-bed reactor zone temperature, hydrogen was replaced at room temperature until a fixed bed reactor air It is completely replaced by hydrogen; 2) introducing hydrogen, while the fixed bed reactor was raised at a heating rate of 5tVmin 35 (TC temperature and at 350 ° C for 3-5 hours until the Ru-M〇0x / AC or Ru-of MoOx from room temperature / CNT multifunctional catalyst sufficiently reduced; 3) the fixed bed reactor temperature was lowered to set 反应温度140-300°C,将浓度为5-30wt%糖醇水溶液与氢气按体积流量比1:50-1:200并流进入固定床反应器,控制液体空速为1. 〇-1〇. 〇h_1和氢气压力2-lOMPa,使糖醇水溶液在固定床反应器内发生蒸发-冷凝反复交替的多相态下在Ru-M〇0x/AC或Ru-MoOx/CNT催化剂表面选择性脱氧反应转化为戊醇和己醇; 4) 从固定床反应器出口排出的气液混合物经2-10MPa高压冷凝,分离为液体产物和不凝性气体产物,液体产物分层为油相和水相,油相为戊醇和己醇的混合物;水相用于水解工艺制备水解糖醇液,气相主要为未参与反应的过量氢气,经循环压缩机增压后再次进入固定床反应器循环利用。 The reaction temperature is 140-300 ° C, a concentration of 5-30wt% aqueous solution of a sugar alcohol with hydrogen by volume flow ratio of 1: 50-1: 200 and flow into a fixed bed reactor, controlling LHSV 1. square-1〇 . 〇h_1 and a hydrogen pressure of 2-lOMPa, sugar alcohol solution evaporation occurs in a fixed bed reactor - the selective Ru-deoxy M〇0x / AC or Ru-MoOx / CNT catalyst surface condensed alternately repeated multiphase the reaction is converted to alcohol, amyl alcohol and hexyl; 4) is discharged from the fixed bed reactor via the gas-liquid mixture outlet 2-10MPa high pressure condensed liquid product and separating non-condensable gas product, the liquid product was stratified into the oil phase and an aqueous phase, the mixture pentanol and hexanol as an oil phase; aqueous phase hydrolysis process for the preparation of hydrolyzed sugar alcohol solution, gas phase mainly the unreacted excess hydrogen gas, into the pressurized recycle compressor through a fixed bed reactor again recycled.
2. 根据权利要求1所述的多相态制备高级一元醇生物燃料的方法,其特征在于,所述Ru-M〇0x/AC催化剂的制备方法如下:椰壳活性炭采用硝酸浸泡12小时,而后用去离子水清洗,反复浸泡和清洗3次,除去椰壳活性炭中的盐分;而后在处理后的椰壳活性炭上负载30wt %Mo〇2,干燥后二次负载3wt % Ru,制备出Ru-Mo0x/AC催化剂。 The method of preparing multiphase higher monohydric alcohols biofuels according to claim 1, characterized in that the preparation of Ru-M〇0x / AC catalyst was as follows: coconut shell activated carbon using nitrate soak 12 hours and then washed with deionized water, soaking and repeatedly washed three times to remove the salt coconut shell activated carbon; 30wt% Mo〇2 then load on coconut shell activated carbon treated, and dried secondary load 3wt% Ru, prepared Ru- Mo0x / AC catalyst.
3. 根据权利要求1所述的多相态制备高级一元醇生物燃料的方法,其特征在于,所述Ru-MoOx/CNT催化剂的制备方法如下:多壁碳纳米管采用硝酸浸泡12小时,而后采用去离子水清洗,反复浸泡和清洗3次,除去多壁碳纳米管中的金属组分;而后在处理后多壁碳纳米管上负载30wt % Mo〇2,干燥后二次负载2wt % RU,制备出RU-M〇0x/CNT催化剂。 The method of preparing multiphase higher monohydric alcohols biofuels according to claim 1, characterized in that the preparation of Ru-MoOx / CNT catalyst was as follows: Multi-walled carbon nanotubes soaked 12 hours using nitric acid, and then washed with deionized water, soaking and repeatedly washed three times to remove the metal components of the multi-walled carbon nanotubes; 30wt% then the load on the MWCNT Mo〇2 workup, drying the secondary load 2wt% RU prepared RU-M〇0x / CNT catalyst.
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