WO2015032237A1 - Method and apparatus for preparing mixed alcohol liquid fuel from aqueous phase bio-oil - Google Patents

Method and apparatus for preparing mixed alcohol liquid fuel from aqueous phase bio-oil Download PDF

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Publication number
WO2015032237A1
WO2015032237A1 PCT/CN2014/080907 CN2014080907W WO2015032237A1 WO 2015032237 A1 WO2015032237 A1 WO 2015032237A1 CN 2014080907 W CN2014080907 W CN 2014080907W WO 2015032237 A1 WO2015032237 A1 WO 2015032237A1
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oil
bio
aqueous
catalytic hydrogenation
mixed alcohol
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PCT/CN2014/080907
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French (fr)
Chinese (zh)
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肖睿
张会岩
陈星�
沈德魁
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东南大学
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Publication of WO2015032237A1 publication Critical patent/WO2015032237A1/en

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    • 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
    • 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
    • C07C29/17Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/177Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group
    • 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
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/582Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to the field of utilization of biomass resources, and in particular to a method and a device for preparing a mixed alcohol liquid fuel from an aqueous phase bio-oil.
  • Biomass is the only renewable carbon source that can be converted into high-grade gas and liquid fuels through a variety of technical means, which is highly compatible with existing fossil fuel technologies.
  • the use of biomass energy can achieve zero emissions of co 2 without causing greenhouse effect problems. It is an important part of China's strategy to improve energy structure and achieve carbon emission reduction targets by vigorously opening up material energy and helping to reduce pollution caused by fossil energy.
  • Biomass rapid pyrolysis technology for the preparation of liquid fuel technology has developed rapidly in recent years with its unique advantages. It can convert biomass into a liquid fuel biomass rapid pyrolysis oil (hereinafter referred to as "bio-oil”) that is easy to store, transport, and has high energy density in a continuous process and factory production mode. Biomass rapid pyrolysis technology has received extensive attention at home and abroad.
  • Bio-oil prepared by rapid pyrolysis of biomass is generally divided into a water-soluble phase (called aqueous phase bio-oil) and a water-insoluble phase bio-oil (called oil-phase bio-oil), in which more than 60% of the carbon in the liquid product is in the aqueous organism.
  • aqueous phase bio-oil water-soluble phase
  • oil-phase bio-oil water-insoluble phase bio-oil
  • the aqueous bio-oil obtained from direct pyrolysis of biomass still has the disadvantages of high moisture content, high viscosity and low calorific value. At present, it can only be applied in boiler fuel with lower requirements. In order to expand its application range, it must be Perform refining treatment.
  • the aqueous phase bio-oil quality improvement process mainly includes physical methods and thermochemical (catalytic) methods.
  • the physical methods include emulsification method and fractionation refining method, which can adjust and improve the characteristics of the aqueous bio-oil at a lower cost to a certain extent, and realize the effective separation and application of the organic components of the aqueous phase bio-oil, but the essential problem remains unsolved.
  • the disadvantages of high water content, low calorific value and poor thermal stability of the aqueous bio-oil cannot be fundamentally changed.
  • thermochemical (catalytic) method mainly includes aqueous phase bio-oil catalytic cracking method and aqueous phase bio-oil catalytic hydrogenation method, and catalytic cracking is carried out by cracking aqueous phase bio-oil under the action of a catalyst to obtain a light oil; aqueous phase bio-oil catalysis
  • the hydrogenation method can partially deoxidize the aqueous phase bio-oil, saturate the unsaturated bond, increase the proportion of the target product such as mixed alcohol in the liquid product, and have high carbon conversion rate, and obtain high-quality biomass-based liquid fuel and high-value platform compound.
  • the method of selective hydrogenation and zeolite catalytic cracking reaction can convert unstable acids, aldehydes, ketones and saccharides in aqueous bio-oil into mixed alcohol-stabilizing compounds and improve aqueous bio-oil. Calorific value, obtaining higher quality liquid fuels and chemicals.
  • aqueous bio-oils Studies on the physicochemical properties of aqueous bio-oils have shown that the pH of aqueous bio-oils is low (about 2 to 3) because it contains a large amount of acidic substances, mainly low-grade carboxylic acids such as acetic acid and formic acid. Acidic application to aqueous bio-oil is extremely Benefits not only increase the cost of storage and transportation, but also corrode processes such as hydrogenation processes and the main components of the burner. In the process of hydrogenation of aqueous bio-oil, carboxylic acid is also the least active component of catalytic hydrogenation reaction, which needs to be converted under high pressure and excess hydrogen.
  • the object of the present invention is to provide an apparatus for firstly synthesizing an aqueous phase bio-oil, and then catalytically hydrogenating the esterified product to obtain a mixed alcohol liquid fuel, and providing a preparation of the mixed alcohol liquid fuel by using the device.
  • the method solves the problems that the reaction of the carboxylic acid component in the aqueous phase bio-oil is poor in the process of upgrading the hydrogenation quality of the aqueous phase bio-oil in the prior art, and the process conditions of the catalytic hydrogenation are demanding.
  • the present invention adopts the following technical solutions:
  • An apparatus for preparing a mixed alcohol liquid fuel by using an aqueous phase bio-oil comprising an aqueous phase bio-oil esterification system, a medium-temperature catalytic hydrogenation system, and a separation and purification system;
  • the aqueous bio-oil esterification system comprising aqueous bio-oil a storage tank, an aqueous bio-oil pump and an esterification reactor, wherein the outlet of the aqueous bio-oil storage tank is connected to the inlet of the aqueous bio-oil pump, and the outlet of the aqueous bio-oil pump is connected to the aqueous bio-oil inlet of the esterification reactor, and the esterification reaction
  • the outlet is connected to an intermediate temperature catalytic hydrogenation reactor esterification product inlet;
  • the intermediate temperature catalytic hydrogenation system comprises a hydrogen storage tank, a hydrogen compressor, a medium temperature catalytic hydrogenation reactor, a solid-liquid separation device, a catalyst regeneration device
  • the hydrogen storage tank outlet is connected to the hydrogen compressor inlet, the hydrogen compressor outlet is connected to the intermediate temperature catalytic hydrogenation reactor hydrogen inlet, and the intermediate temperature catalytic hydrogenation reactor hydrogenation product outlet is connected to the inlet of the solid-liquid separation device, solid-liquid separation
  • the solid phase outlet of the device is connected to the inlet of the catalyst regeneration device, and the outlet of the catalyst regeneration device is connected to the inlet of the catalyst storage tank.
  • the catalyst storage tank outlet is connected to the intermediate temperature catalytic hydrogenation reactor catalyst inlet, and the solid-liquid separation device gas phase outlet is connected to the gas-liquid separator inlet;
  • the separation and purification system comprises a gas-liquid separator, a sampling detection point and a mixed alcohol flow dividing device.
  • the gas-liquid separator outlet is connected to the inlet of the mixed alcohol splitting device
  • the sampling detecting point is disposed between the gas-liquid separator outlet and the inlet of the mixed alcohol splitting device
  • the mixed alcohol splitting device is provided with a reflux outlet and a product outlet, and the mixed alcohol splitting
  • the reflux outlet of the unit is connected to the alcohol inlet of the esterification reactor.
  • the method for preparing a mixed alcohol liquid fuel by using the above device for the aqueous phase bio-oil comprises the following steps: Step 1: esterifying the aqueous phase bio-oil raw material to convert the organic acid in the aqueous phase bio-oil raw material into an ester: The aqueous phase bio-oil raw material in the aqueous bio-oil storage tank is pressed into the esterification reactor through the aqueous phase bio-oil pump, and the organic acid in the aqueous bio-oil raw material is esterified with the introduced alcohol, and the organic acid is converted.
  • Step 2 catalytic hydrogenation of the esterified product at a medium temperature condition: the hydrogen in the hydrogen storage tank is pressurized by a hydrogen compressor, and is passed to a medium-temperature catalytic hydrogenation reactor.
  • the esterified aqueous phase bio-oil and the catalyst obtained in the first step are respectively added, and after the three-phase catalytic hydrogenation reaction, the solid-liquid product formed is introduced into the solid-liquid separation device; the solid-liquid separation device separates the solid phase product, that is, the catalyst, Catalyst
  • the catalyst regeneration device is sent to remove the surface area carbon of the catalyst, and the regenerated catalyst is sent to the catalyst storage tank for storage, and then sent to the intermediate temperature catalytic hydrogenation reactor for recycling; the solid-liquid separation device separates the liquid phase product in the solid liquid
  • the separation device is heated and evaporated to become a gas phase product;
  • Step 3 separating and purifying to obtain a mixed alcohol liquid fuel: the gas phase product produced in the second step is sent to the gas-liquid separator, after cooling, fractionating, purifying, and condensing the liquid phase
  • the product is a mixed alcohol product, the non-condensable gas is the tail gas generated by the reaction and a part of unreacted hydrogen; after
  • the esterification reactor has an operating temperature of 150 280 V and a working pressure of 6-10 MPa.
  • the medium temperature catalytic hydrogenation reactor has an operating temperature of 100 240 V and a working pressure of 5-8 MPa; the three-phase catalytic hydrogenation reaction is carried out in a slurry bed; and the catalyst is a nickel-based molecular sieve.
  • the carboxylic acid component in the aqueous phase bio-oil causes the stability of the aqueous phase bio-oil to be not high, the reaction activity in the catalytic conversion process is poor, and the catalytic hydrogenation process conditions are demanding.
  • the method of the present invention firstly carries out the aqueous phase bio-oil raw material. Esterification treatment, converting carboxylic acid components in aqueous bio-oil into neutral esters, reducing the acidity of aqueous bio-oil, improving the stability of aqueous bio-oil and catalytic hydrogenation, compared to traditional aqueous organisms
  • the oil catalytic hydrogenation process greatly increases the yield of the mixed alcohol.
  • esterification pretreatment is an effective means to reduce corrosion, improve stability and reduce viscosity.
  • the prepared mixed liquid liquid fuel product is split, and a part of the mixed alcohol is refluxed into the esterification reactor to be used as a raw material for esterifying the aqueous phase bio-oil to realize recycling of the raw material-product. It saves the cost of purchasing alcohol raw materials, reduces material and energy consumption, reduces waste emissions, and realizes a green and recycling process.
  • the invention utilizes a slurry bed to carry out catalytic hydrogenation of aqueous phase bio-oil to obtain a mixed alcohol liquid fuel under medium temperature conditions, compared with the traditional fixed bed aqueous phase bio-oil catalytic hydrogenation technology, "solid (catalyst), liquid (Aqueous phase bio-oil), gas (hydrogen) "Three-phase blending and co-refining in a slurry bed", the contact area of the three-phase reaction is large and the contact time is long, and the efficiency of catalytic hydrogenation will be significantly improved (ie carbon conversion)
  • the high rate and high yield of the target product effectively reducing the reaction conditions of catalytic hydrogenation, such as temperature and pressure, the time of the entire process will be greatly shortened.
  • FIG. 1 is a schematic view showing the apparatus for preparing a mixed alcohol liquid fuel according to the aqueous phase bio-oil of the present invention.
  • Aqueous bio-oil esterification system I medium-temperature catalytic hydrogenation system II, separation and purification system III; aqueous bio-oil storage tank 1, aqueous bio-oil pump 2, esterification reactor 3, hydrogen storage tank 4, hydrogen compressor 5.
  • aqueous bio-oil storage tank 1 aqueous bio-oil pump 2
  • esterification reactor 3 hydrogen storage tank 4
  • hydrogen compressor 5 hydrogen compressor 5.
  • a device for preparing a mixed alcohol liquid fuel by using an aqueous phase bio-oil comprising: an aqueous phase bio-oil esterification system I for esterifying an aqueous phase bio-oil feedstock to reduce aqueous bio-oil Acidity, improve the stability of aqueous bio-oil; Medium-temperature catalytic hydrogenation system II, used to receive the esterification product of hydrogen and aqueous bio-oil esterification system I, and undergo catalytic hydrogenation reaction under the action of catalyst to form hydrogenated gas phase product Separation and purification system III for receiving the hydrogenated gas phase product of the intermediate temperature catalytic hydrogenation system II, separating and purifying to obtain a mixed alcohol liquid fuel, and feeding a part of the mixed alcohol into the aqueous phase bio-oil esterification system I for circulation use.
  • an aqueous phase bio-oil esterification system I for esterifying an aqueous phase bio-oil feedstock to reduce aqueous bio-oil
  • the aqueous phase bio-oil esterification system 1 comprises an aqueous phase bio-oil storage tank 1, an aqueous phase bio-oil pump 2 and an esterification reactor 3, wherein the outlet of the aqueous-phase bio-oil storage tank 1 is connected to the inlet of the aqueous bio-oil pump 2, The outlet of the aqueous bio-oil pump 2 is connected to the aqueous phase bio-oil inlet of the esterification reactor 3, and the outlet of the esterification reactor 3 is connected to the inlet of the esterification product of the intermediate-temperature catalytic hydrogenation reactor 6.
  • the intermediate temperature catalytic hydrogenation system II comprises a hydrogen storage tank 4, a hydrogen compressor 5, an intermediate temperature catalytic hydrogenation reactor 6, a solid-liquid separation device 7, a catalyst regeneration device 8, and a catalyst storage tank 9, wherein the hydrogen storage tank 4 outlet Connected to the inlet of the hydrogen compressor 5, the outlet of the hydrogen compressor 5 is connected to the hydrogen inlet of the intermediate temperature catalytic hydrogenation reactor 6, and the outlet of the hydrogenation product of the intermediate temperature catalytic hydrogenation reactor 6 is connected to the inlet of the solid-liquid separation device 7, the solid-liquid separation device 7
  • the solid phase outlet is connected to the inlet of the catalyst regeneration device 8, the outlet of the catalyst regeneration device 8 is connected to the inlet of the catalyst storage tank 9, and the outlet of the catalyst storage tank 9 is connected to the catalyst inlet of the intermediate temperature catalytic hydrogenation reactor 6, and the gas phase outlet of the solid-liquid separation device 7 is The gas-liquid separator 10 is connected at the inlet.
  • the separation and purification system III comprises a gas-liquid separator 10, a sampling detection point 11 and a mixed alcohol splitting device 12, wherein the outlet of the gas-liquid separator 10 is connected to the inlet of the mixed alcohol splitting device 12, and the sampling detecting point 11 is set in the gas-liquid Between the separator 10 outlet and the inlet of the mixed alcohol splitting unit 12, the mixed alcohol splitting unit 12 is provided with a reflux outlet and a product outlet, wherein the reflux outlet is connected to the alcoholation reactor 3 alcohol inlet.
  • the method for preparing a mixed alcohol liquid fuel by using the above-mentioned device comprises the following steps: Step 1: esterifying the aqueous phase bio-oil raw material to convert the organic acid in the aqueous phase bio-oil raw material into an ester:
  • the aqueous phase bio-oil raw material in the aqueous bio-oil storage tank 1 is pressed into the esterification reactor 3 through the aqueous bio-oil pump 2, and the organic acid in the aqueous bio-oil raw material is esterified with the introduced alcohol, and organic
  • the acid is converted into an ester, the acidity of the aqueous phase bio-oil is lowered, and the stability is improved, wherein the esterification reactor 3 has an operating temperature of 150 280 ° C and a working pressure of 6 to 10 MPa;
  • Step 2 at a medium temperature, the ester Catalytic hydrogenation of chemical products:
  • the hydrogen in the hydrogen storage tank 4 is pressurized by the hydrogen compressor 5, and is introduced into the intermediate temperature catalytic hydrogenation reactor 6 while being separately added.
  • the solid-liquid product formed is passed into the solid-liquid separation device 7, wherein the medium-temperature catalytic hydrogenation
  • the reactor 6 has an operating temperature of 100 240 ° C and a working pressure of 5 to 8 MPa.
  • the solid-liquid separation device 7 separates the solid phase product, that is, the catalyst, and sends the catalyst to the catalyst regeneration device 8 to remove the catalyst surface area carbon and the regenerated catalyst.
  • the solid-liquid separation device 7 separates the liquid phase product and is heated and evaporated in the solid-liquid separation device 7 to become a gas phase product. ;
  • Step 3 Separating and purifying to obtain a mixed alcohol liquid fuel:
  • the gas phase product produced in the second step is sent to the gas-liquid separator 10, and after cooling, fractionation and purification, the condensed liquid phase product is a mixed alcohol product, and the non-condensed gas is the tail gas generated by the reaction and a part of unreacted hydrogen;
  • the mixed alcohol product is sampled and tested at the sampling test point 11, it is passed to the mixed alcohol splitting device 12, and a part of the mixed alcohol is sent to the esterification reactor 3 as an aqueous phase bio-oil raw material esterification treatment station.
  • the required alcohol raw materials are recycled; the remaining mixed alcohols are the product mixed alcohol liquid fuels.
  • aqueous phase bio-oil raw materials used in the examples are from a company in Shandong, which contains the following percentages: alcohols 3%, esters 3%, ethers 4%, ketones 16%, and phenols 12 %, acid accounted for 38%, aldehydes accounted for 11%, and other components accounted for 13%.
  • the method for preparing a mixed alcohol liquid fuel by using the apparatus shown in Fig. 1 comprises the following steps: Step 1: esterifying the aqueous phase bio-oil raw material to convert the organic acid in the aqueous phase bio-oil raw material into an ester Class: 40 g of aqueous bio-oil raw material in the aqueous bio-oil storage tank 1 is pressed into the esterification reactor 3 through the aqueous bio-oil pump 2, firstly using methanol and aqueous bio-oil according to the quality without preparing the mixed alcohol.
  • the ratio is 3: 1 feed mixing, maintaining the reaction temperature is 240 V, the pressure is 8 MPa, the organic acid and alcohol in the aqueous bio-oil are esterified, the reaction is complete, the organic acid is converted into ester, water phase Bio-oil has reduced acidity and improved stability.
  • Step 2 catalytic hydrogenation of the esterification product by using a slurry bed at a medium temperature condition:
  • 60 mL of hydrogen in the hydrogen storage tank 4 is pressurized by the hydrogen compressor 5, and is introduced into the intermediate temperature catalytic hydrogenation reactor 6, and simultaneously added the aqueous phase bio-oil and the 2 g nickel-based molecular sieve catalyst M-step after the esterification treatment.
  • HZSM-5 maintaining a reaction temperature of 140 V and a pressure of 6 MPa, the reaction is complete; after three-phase catalytic hydrogenation reaction, the solid-liquid product, that is, the hydrogenated product, is introduced into the solid-liquid separation device 7, wherein the three-phase finger Solid phase: catalyst, liquid phase: esterified aqueous bio-oil, gas phase: hydrogen; solid-liquid separation device (volatiles) 12 Separation of solid phase product, ie catalyst; then catalyst is sent to catalyst regeneration unit 8, to remove catalyst surface area carbon The regenerated catalyst is sent to the catalyst storage tank 8 for storage and finally sent The intermediate temperature catalytic hydrogenation reactor 6 is recycled, and the liquid phase product is heated and evaporated in a solid-liquid separation device (volatiles) 12 to become a gas phase product.
  • Step 3 Separating and purifying to obtain a mixed alcohol liquid fuel:
  • the gas phase product produced in the second step is sent to the gas-liquid separator 10, and after cooling, fractionation and purification, the condensed liquid phase product is a mixed alcohol product, and the non-condensed gas is the tail gas generated by the reaction and a part of unreacted hydrogen;
  • the mixed alcohol product is sampled and tested at the sampling test point 11, it is passed to the mixed alcohol splitting device 12, and a part of the mixed alcohol is sent to the esterification reactor 3 as required for esterification of the aqueous phase bio-oil.
  • the alcohol raw material is recycled, and the remaining product is used as a mixed alcohol liquid fuel.
  • reaction temperature of step 1 is 150 V and the pressure is 6 MPa ; the reaction temperature of step 2 is 100 V, and the pressure is 5 MPa.
  • the above method is used to carry out esterification and hydrogenation of the aqueous phase bio-oil raw materials, as follows: the mass fraction of each component in the aqueous bio-oil raw material is as follows: alcohol accounts for 3%, ester accounts for 3%, and ether accounts for 4%, ketones accounted for 16%, phenols accounted for 12%, acids accounted for 38%, aldehydes accounted for 11%, other components accounted for 13%; after esterification, alcohol accounted for 47%, esters accounted for 18%, Ethers accounted for 3%, ketones accounted for 8%, phenols accounted for 7%, aldehydes accounted for 5%, acids accounted for 12%; after catalytic hydrogenation, alcohols accounted for 62%, esters accounted for 14%, ethers 3%, ketones accounted for 4%, phenols accounted for 5%, aldehydes accounted for 5%, and acids accounted for 7%.
  • reaction temperature in step 1 is 280 ° C and the pressure is 10 MPa; the reaction temperature in step 2 is 240 V and the pressure is 8 MPa.
  • the above method is used to carry out esterification and hydrogenation of the aqueous phase bio-oil raw materials, as follows: the mass fraction of each component in the aqueous bio-oil raw material is as follows: alcohol accounts for 3%, ester accounts for 3%, and ether accounts for 4%, ketones accounted for 16%, phenols accounted for 12%, acids accounted for 38%, aldehydes accounted for 11%, other components accounted for 13%; after esterification, alcohol accounted for 71%, esters accounted for 17%, Ethers accounted for 2%, ketones accounted for 3%, phenols accounted for 6%, and acids accounted for 1%.

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Abstract

An apparatus for preparing mixed alcohol liquid fuel from aqueous phase bio-oil. The apparatus comprises an esterification system (I) of the aqueous phase bio-oil, a moderate temperature catalytic hydrogenation system (II) and a separation and purification system (III). A method for preparing the mixed alcohol liquid fuel from the aqueous phase bio-oil by using the above-mentioned apparatus. The method comprises the following steps: esterifying aqueous phase bio-oil raw material; performing catalytic hydrogenation on esterification products under moderate temperature; obtaining mixed alcohol liquid fuel after separation and purification. In the method, the aqueous phase bio-oil raw material is firstly esterified to reduce the acidity of the aqueous phase bio-oil, and the stability and the catalytic hydrogenation reactivity of the aqueous phase bio-oil are increased.

Description

一种水相生物油制备混合醇类液体燃料的方法和装置 技术领域  Method and device for preparing mixed alcohol liquid fuel by using aqueous phase bio-oil
本发明涉及生物质资源利用领域,具体涉及一种水相生物油制备混合醇类液体燃料的方 法和装置。  The invention relates to the field of utilization of biomass resources, and in particular to a method and a device for preparing a mixed alcohol liquid fuel from an aqueous phase bio-oil.
背景技术 Background technique
生物质能是唯一一种可再生碳源,它能够通过多种技术途径转化成高品位的气体和液体 燃料, 与现有化石燃料技术具有很大的兼容性。 此外, 利用生物质能可以实现 co2的零排 放, 不会带来温室效应问题。 大力开发生物质能, 有利于减轻化石能源带来的污染, 是我国 改善能源结构,实现碳减排目标战略的重要组成部分。生物质快速热裂解技术制备液体燃料 技术以其独特的优势近年来得到了迅速发展。它能以连续的工艺和工厂化生产方式将生物质 转化成易储存、易运输、能量密度高的液体燃料 生物质快速热解油(以下简称"生物油")。 生物质快速热裂解技术已受到国内外的广泛关注。 Biomass is the only renewable carbon source that can be converted into high-grade gas and liquid fuels through a variety of technical means, which is highly compatible with existing fossil fuel technologies. In addition, the use of biomass energy can achieve zero emissions of co 2 without causing greenhouse effect problems. It is an important part of China's strategy to improve energy structure and achieve carbon emission reduction targets by vigorously opening up material energy and helping to reduce pollution caused by fossil energy. Biomass rapid pyrolysis technology for the preparation of liquid fuel technology has developed rapidly in recent years with its unique advantages. It can convert biomass into a liquid fuel biomass rapid pyrolysis oil (hereinafter referred to as "bio-oil") that is easy to store, transport, and has high energy density in a continuous process and factory production mode. Biomass rapid pyrolysis technology has received extensive attention at home and abroad.
生物质快速热解制备的生物油一般分为水溶相 (称为水相生物油)和水不溶相生物油(称 为油相生物油), 其中液体产物中 60%以上的碳在水相生物油中, 因此水相生物油具有较高 的应用价值。然而从生物质直接热解获得的水相生物油仍然具有水分含量高、粘度高、热值 低的缺点, 目前只能在要求较低的锅炉燃油中应用,为了扩大它的应用范围必须对其进行精 制处理。 水相生物油品质提升工艺主要有物理方法和热化学(催化)法。物理方法有乳化法 和分馏精制法,可以在一定程度上以较低成本调整与改善水相生物油特性,实现对水相生物 油有机组分的有效分离与应用,但是本质问题仍然没有解决,不能从根本上改变水相生物油 含氧量高、 热值低以及热稳定性差的缺点。 热化学(催化)方法主要有水相生物油催化裂化 法以及水相生物油催化加氢法,催化裂化是通过将水相生物油在催化剂作用下裂解以获得轻 质油; 水相生物油催化加氢的方法可以对水相生物油进行部分脱氧、饱和不饱和键、提升液 体产物中混合醇等目标产物比例且碳转化率高,获得高品质生物质基液体燃料以及高价值平 台化合物。采用选择性加氢和沸石催化裂解反应耦合的方法,能将水相生物油中不稳定的酸 类、醛类、 酮类和糖类等化合物转化为混合醇类稳定化合物, 提高水相生物油热值, 获得较 高品质的液体燃料与化学品。  Bio-oil prepared by rapid pyrolysis of biomass is generally divided into a water-soluble phase (called aqueous phase bio-oil) and a water-insoluble phase bio-oil (called oil-phase bio-oil), in which more than 60% of the carbon in the liquid product is in the aqueous organism. In oil, therefore, aqueous bio-oil has a high application value. However, the aqueous bio-oil obtained from direct pyrolysis of biomass still has the disadvantages of high moisture content, high viscosity and low calorific value. At present, it can only be applied in boiler fuel with lower requirements. In order to expand its application range, it must be Perform refining treatment. The aqueous phase bio-oil quality improvement process mainly includes physical methods and thermochemical (catalytic) methods. The physical methods include emulsification method and fractionation refining method, which can adjust and improve the characteristics of the aqueous bio-oil at a lower cost to a certain extent, and realize the effective separation and application of the organic components of the aqueous phase bio-oil, but the essential problem remains unsolved. The disadvantages of high water content, low calorific value and poor thermal stability of the aqueous bio-oil cannot be fundamentally changed. The thermochemical (catalytic) method mainly includes aqueous phase bio-oil catalytic cracking method and aqueous phase bio-oil catalytic hydrogenation method, and catalytic cracking is carried out by cracking aqueous phase bio-oil under the action of a catalyst to obtain a light oil; aqueous phase bio-oil catalysis The hydrogenation method can partially deoxidize the aqueous phase bio-oil, saturate the unsaturated bond, increase the proportion of the target product such as mixed alcohol in the liquid product, and have high carbon conversion rate, and obtain high-quality biomass-based liquid fuel and high-value platform compound. The method of selective hydrogenation and zeolite catalytic cracking reaction can convert unstable acids, aldehydes, ketones and saccharides in aqueous bio-oil into mixed alcohol-stabilizing compounds and improve aqueous bio-oil. Calorific value, obtaining higher quality liquid fuels and chemicals.
对水相生物油物化特性的研究表明, 水相生物油的 pH值较低 (2〜3左右), 这是因其 含有大量酸性物质, 主要是低级羧酸类, 如乙酸和甲酸等。酸性对水相生物油的应用极其不 利, 不仅会增加储存和运输的成本, 而且会腐蚀处理过程(如加氢过程)和燃烧器的主要部 件。在水相生物油加氢过程中, 羧酸也是催化加氢反应活性最差的组分, 需要在高压、过量 氢气条件下才能转化。 Studies on the physicochemical properties of aqueous bio-oils have shown that the pH of aqueous bio-oils is low (about 2 to 3) because it contains a large amount of acidic substances, mainly low-grade carboxylic acids such as acetic acid and formic acid. Acidic application to aqueous bio-oil is extremely Benefits not only increase the cost of storage and transportation, but also corrode processes such as hydrogenation processes and the main components of the burner. In the process of hydrogenation of aqueous bio-oil, carboxylic acid is also the least active component of catalytic hydrogenation reaction, which needs to be converted under high pressure and excess hydrogen.
发明内容 Summary of the invention
本发明的目的在于提供一种先对水相生物油进行酯化处理,再对酯化产物催化加氢制取 混合醇类液体燃料装置,并提供了利用该装置进行混合醇类液体燃料的制备方法,解决现有 技术中水相生物油加氢品质提升过程中,水相生物油中羧酸类成分造成的反应活性差,催化 加氢工艺条件要求苛刻等问题。  The object of the present invention is to provide an apparatus for firstly synthesizing an aqueous phase bio-oil, and then catalytically hydrogenating the esterified product to obtain a mixed alcohol liquid fuel, and providing a preparation of the mixed alcohol liquid fuel by using the device. The method solves the problems that the reaction of the carboxylic acid component in the aqueous phase bio-oil is poor in the process of upgrading the hydrogenation quality of the aqueous phase bio-oil in the prior art, and the process conditions of the catalytic hydrogenation are demanding.
为解决上述问题, 本发明采用以下技术方案:  In order to solve the above problems, the present invention adopts the following technical solutions:
一种水相生物油制备混合醇类液体燃料的装置,它包括水相生物油酯化系统、中温催化 加氢系统和分离与提纯系统;所述水相生物油酯化系统包括水相生物油储罐、水相生物油泵 和酯化反应器, 其中, 水相生物油储罐出口与水相生物油泵入口相连, 水相生物油泵出口与 酯化反应器水相生物油入口相连, 酯化反应器出口与中温催化加氢反应器酯化产物入口相 连; 所述中温催化加氢系统包括氢气储罐、氢气压缩机、 中温催化加氢反应器、 固液分离装 置、催化剂再生装置和催化剂储槽, 其中, 氢气储罐出口与氢气压缩机入口相连, 氢气压缩 机出口与中温催化加氢反应器氢气入口相连,中温催化加氢反应器加氢产物出口与固液分离 装置入口相连, 固液分离装置固相出口与催化剂再生装置入口相连,催化剂再生装置出口与 催化剂储槽入口相连,催化剂储槽出口再与中温催化加氢反应器催化剂入口相连, 固液分离 装置气相出口与气液分离器入口相连;所述分离与提纯系统包括气液分离器、抽样检测点和 混合醇分流装置, 其中, 气液分离器出口与混合醇分流装置入口相连, 抽样检测点设置在气 液分离器出口和混合醇分流装置入口之间,混合醇分流装置设有回流出口和产物出口,混合 醇分流装置回流出口与酯化反应器醇类入口相连。  An apparatus for preparing a mixed alcohol liquid fuel by using an aqueous phase bio-oil, comprising an aqueous phase bio-oil esterification system, a medium-temperature catalytic hydrogenation system, and a separation and purification system; the aqueous bio-oil esterification system comprising aqueous bio-oil a storage tank, an aqueous bio-oil pump and an esterification reactor, wherein the outlet of the aqueous bio-oil storage tank is connected to the inlet of the aqueous bio-oil pump, and the outlet of the aqueous bio-oil pump is connected to the aqueous bio-oil inlet of the esterification reactor, and the esterification reaction The outlet is connected to an intermediate temperature catalytic hydrogenation reactor esterification product inlet; the intermediate temperature catalytic hydrogenation system comprises a hydrogen storage tank, a hydrogen compressor, a medium temperature catalytic hydrogenation reactor, a solid-liquid separation device, a catalyst regeneration device, and a catalyst storage tank. Wherein, the hydrogen storage tank outlet is connected to the hydrogen compressor inlet, the hydrogen compressor outlet is connected to the intermediate temperature catalytic hydrogenation reactor hydrogen inlet, and the intermediate temperature catalytic hydrogenation reactor hydrogenation product outlet is connected to the inlet of the solid-liquid separation device, solid-liquid separation The solid phase outlet of the device is connected to the inlet of the catalyst regeneration device, and the outlet of the catalyst regeneration device is connected to the inlet of the catalyst storage tank. The catalyst storage tank outlet is connected to the intermediate temperature catalytic hydrogenation reactor catalyst inlet, and the solid-liquid separation device gas phase outlet is connected to the gas-liquid separator inlet; the separation and purification system comprises a gas-liquid separator, a sampling detection point and a mixed alcohol flow dividing device. Wherein, the gas-liquid separator outlet is connected to the inlet of the mixed alcohol splitting device, the sampling detecting point is disposed between the gas-liquid separator outlet and the inlet of the mixed alcohol splitting device, and the mixed alcohol splitting device is provided with a reflux outlet and a product outlet, and the mixed alcohol splitting The reflux outlet of the unit is connected to the alcohol inlet of the esterification reactor.
利用上述装置进行水相生物油制备混合醇类液体燃料的方法, 它包括以下步骤: 步骤一、将水相生物油原料进行酯化, 使水相生物油原料中的有机酸转化为酯类: 将水 相生物油储罐中的水相生物油原料通过水相生物油泵压入酯化反应器,水相生物油原料中的 有机酸和通入的醇类发生酯化反应, 有机酸被转化为酯类, 得到酯化水相生物油; 步骤二、 在中温条件下, 对酯化产物催化加氢: 氢气储罐中的氢气经氢气压缩机加压, 通入中温催化 加氢反应器, 同时分别加入步骤一得到的酯化水相生物油和催化剂,经过三相催化加氢反应 后, 生成的固液产物通入固液分离装置; 固液分离装置分离出固相产物即催化剂, 将催化剂 送入催化剂再生装置, 去除催化剂表面积炭, 再生后的催化剂被送入催化剂储槽中储存, 再 被送入中温催化加氢反应器进行循环使用;固液分离装置分离出液相产物在固液分离装置中 被加热蒸发而变成气相产物; 步骤三、分离提纯得到混合醇类液体燃料: 将步骤二生成的气 相产物送入气液分离器, 经过冷却、 分馏、 提纯, 冷凝后的液相产物即为混合醇类产物, 不 冷凝气体为反应产生的尾气和部分未反应的氢气;对混合醇类产物在抽样检测点处取样检测 合格后, 将其通入混合醇分流装置, 将一部分混合醇类送入酯化反应器中, 作为水相生物油 原料酯化处理所需的醇类原料, 进行循环利用; 剩余的为产品混合醇类液体燃料。 The method for preparing a mixed alcohol liquid fuel by using the above device for the aqueous phase bio-oil comprises the following steps: Step 1: esterifying the aqueous phase bio-oil raw material to convert the organic acid in the aqueous phase bio-oil raw material into an ester: The aqueous phase bio-oil raw material in the aqueous bio-oil storage tank is pressed into the esterification reactor through the aqueous phase bio-oil pump, and the organic acid in the aqueous bio-oil raw material is esterified with the introduced alcohol, and the organic acid is converted. For esters, an esterified aqueous bio-oil is obtained; Step 2: catalytic hydrogenation of the esterified product at a medium temperature condition: the hydrogen in the hydrogen storage tank is pressurized by a hydrogen compressor, and is passed to a medium-temperature catalytic hydrogenation reactor. At the same time, the esterified aqueous phase bio-oil and the catalyst obtained in the first step are respectively added, and after the three-phase catalytic hydrogenation reaction, the solid-liquid product formed is introduced into the solid-liquid separation device; the solid-liquid separation device separates the solid phase product, that is, the catalyst, Catalyst The catalyst regeneration device is sent to remove the surface area carbon of the catalyst, and the regenerated catalyst is sent to the catalyst storage tank for storage, and then sent to the intermediate temperature catalytic hydrogenation reactor for recycling; the solid-liquid separation device separates the liquid phase product in the solid liquid The separation device is heated and evaporated to become a gas phase product; Step 3: separating and purifying to obtain a mixed alcohol liquid fuel: the gas phase product produced in the second step is sent to the gas-liquid separator, after cooling, fractionating, purifying, and condensing the liquid phase The product is a mixed alcohol product, the non-condensable gas is the tail gas generated by the reaction and a part of unreacted hydrogen; after the mixed alcohol product is sampled and tested at the sampling test point, it is passed to the mixed alcohol flow dividing device, and a part is mixed. The alcohol is fed to the esterification reactor, and is used as an alcohol raw material required for the esterification treatment of the aqueous phase bio-oil feedstock, and is recycled; the remainder is a product mixed with an alcohol-based liquid fuel.
步骤一中, 所述酯化反应器工作温度为 150 280 V, 工作压力为 6~10 MPa。  In the first step, the esterification reactor has an operating temperature of 150 280 V and a working pressure of 6-10 MPa.
步骤二中, 所述中温催化加氢反应器工作温度为 100 240 V, 工作压力为 5~8 MPa; 所述三相催化加氢反应在浆态床中反应; 所述催化剂为镍基分子筛。  In the second step, the medium temperature catalytic hydrogenation reactor has an operating temperature of 100 240 V and a working pressure of 5-8 MPa; the three-phase catalytic hydrogenation reaction is carried out in a slurry bed; and the catalyst is a nickel-based molecular sieve.
本发明的有益效果:  The beneficial effects of the invention:
1.水相生物油中羧酸类成分造成水相生物油稳定性不高, 在催化转化过程中反应活性 差, 对催化加氢工艺条件要求苛刻, 本发明方法先对水相生物油原料进行酯化处理, 将水相 生物油中羧酸类成分转化为中性的酯类, 降低水相生物油酸度,提高水相生物油稳定性和催 化加氢反应活性, 相比于传统水相生物油催化加氢过程, 大大提高了混合醇的收率。 同时酯 化预处理是降低腐蚀性、 提高稳定性、 减小粘度的有效手段。  1. The carboxylic acid component in the aqueous phase bio-oil causes the stability of the aqueous phase bio-oil to be not high, the reaction activity in the catalytic conversion process is poor, and the catalytic hydrogenation process conditions are demanding. The method of the present invention firstly carries out the aqueous phase bio-oil raw material. Esterification treatment, converting carboxylic acid components in aqueous bio-oil into neutral esters, reducing the acidity of aqueous bio-oil, improving the stability of aqueous bio-oil and catalytic hydrogenation, compared to traditional aqueous organisms The oil catalytic hydrogenation process greatly increases the yield of the mixed alcohol. At the same time, esterification pretreatment is an effective means to reduce corrosion, improve stability and reduce viscosity.
2.将制取的混合醇类液体燃料产物进行分流,一部分混合醇类回流入酯化反应器,作为 酯化水相生物油的原料,实现了原料一产物一原料的循环利用。节约了购买醇类原料的成本, 减少物料和能量消耗, 减少废弃物排放, 实现了绿色、 循环工艺。  2. The prepared mixed liquid liquid fuel product is split, and a part of the mixed alcohol is refluxed into the esterification reactor to be used as a raw material for esterifying the aqueous phase bio-oil to realize recycling of the raw material-product. It saves the cost of purchasing alcohol raw materials, reduces material and energy consumption, reduces waste emissions, and realizes a green and recycling process.
3.本发明利用浆态床在中温条件下进行水相生物油催化加氢制取混合醇类液体燃料,与 传统固定床水相生物油催化加氢技术相比, "固 (催化剂)、 液(水相生物油)、 气 (氢气) " 三相在浆态床中"共混共炼", 三相反应的接触面积大且接触时间长,催化加氢的效率将显著 提高 (即碳转化率高且目标产物产率高), 有效降低催化加氢的反应条件, 如温度和压力, 整个工艺流程的时间将大大缩短。  3. The invention utilizes a slurry bed to carry out catalytic hydrogenation of aqueous phase bio-oil to obtain a mixed alcohol liquid fuel under medium temperature conditions, compared with the traditional fixed bed aqueous phase bio-oil catalytic hydrogenation technology, "solid (catalyst), liquid (Aqueous phase bio-oil), gas (hydrogen) "Three-phase blending and co-refining in a slurry bed", the contact area of the three-phase reaction is large and the contact time is long, and the efficiency of catalytic hydrogenation will be significantly improved (ie carbon conversion) The high rate and high yield of the target product), effectively reducing the reaction conditions of catalytic hydrogenation, such as temperature and pressure, the time of the entire process will be greatly shortened.
附图说明 DRAWINGS
图 1是本发明水相生物油制备混合醇类液体燃料装置示意图。  BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the apparatus for preparing a mixed alcohol liquid fuel according to the aqueous phase bio-oil of the present invention.
水相生物油酯化系统 I、中温催化加氢系统 II、分离与提纯系统 III;水相生物油储罐 1、 水相生物油泵 2、 酯化反应器 3、 氢气储罐 4、 氢气压缩机 5、 中温催化加氢反应器 6、 固液 分离装置 7、催化剂再生装置 8、催化剂储槽 9、气液分离器 10、抽样检测点 11和混合醇分 流装置 12。 Aqueous bio-oil esterification system I, medium-temperature catalytic hydrogenation system II, separation and purification system III; aqueous bio-oil storage tank 1, aqueous bio-oil pump 2, esterification reactor 3, hydrogen storage tank 4, hydrogen compressor 5. Medium temperature catalytic hydrogenation reactor 6, solid-liquid separation device 7, catalyst regeneration device 8, catalyst storage tank 9, gas-liquid separator 10, sampling detection point 11 and mixed alcohol Flow device 12.
具体实施方式 detailed description
下面结合附图和实施例对本发明做更进一步的解释。  The invention will be further explained below in conjunction with the drawings and embodiments.
一种水相生物油制备混合醇类液体燃料的装置, 如图 1所示, 包括: 水相生物油酯化系 统 I,用于对水相生物油原料进行酯化处理,降低水相生物油酸度,提高水相生物油稳定性; 中温催化加氢系统 II,用于接收氢气和水相生物油酯化系统 I的酯化产物,在催化剂作用下 经过催化加氢反应, 生成加氢气相产物; 分离与提纯系统 III, 用于接收中温催化加氢系统 II 的加氢气相产物,分离提纯获得混合醇类液体燃料,并将部分混合醇类送入水相生物油酯化 系统 I, 进行循环利用。  A device for preparing a mixed alcohol liquid fuel by using an aqueous phase bio-oil, as shown in FIG. 1, comprising: an aqueous phase bio-oil esterification system I for esterifying an aqueous phase bio-oil feedstock to reduce aqueous bio-oil Acidity, improve the stability of aqueous bio-oil; Medium-temperature catalytic hydrogenation system II, used to receive the esterification product of hydrogen and aqueous bio-oil esterification system I, and undergo catalytic hydrogenation reaction under the action of catalyst to form hydrogenated gas phase product Separation and purification system III for receiving the hydrogenated gas phase product of the intermediate temperature catalytic hydrogenation system II, separating and purifying to obtain a mixed alcohol liquid fuel, and feeding a part of the mixed alcohol into the aqueous phase bio-oil esterification system I for circulation use.
所述水相生物油酯化系统 I包括水相生物油储罐 1、 水相生物油泵 2和酯化反应器 3, 其中,水相生物油储罐 1出口与水相生物油泵 2入口相连,水相生物油泵 2出口与酯化反应 器 3水相生物油入口相连, 酯化反应器 3出口与中温催化加氢反应器 6酯化产物入口相连。  The aqueous phase bio-oil esterification system 1 comprises an aqueous phase bio-oil storage tank 1, an aqueous phase bio-oil pump 2 and an esterification reactor 3, wherein the outlet of the aqueous-phase bio-oil storage tank 1 is connected to the inlet of the aqueous bio-oil pump 2, The outlet of the aqueous bio-oil pump 2 is connected to the aqueous phase bio-oil inlet of the esterification reactor 3, and the outlet of the esterification reactor 3 is connected to the inlet of the esterification product of the intermediate-temperature catalytic hydrogenation reactor 6.
所述中温催化加氢系统 II包括氢气储罐 4、 氢气压缩机 5、 中温催化加氢反应器 6、 固 液分离装置 7、 催化剂再生装置 8和催化剂储槽 9, 其中, 氢气储罐 4出口与氢气压缩机 5 入口相连,氢气压缩机 5出口与中温催化加氢反应器 6氢气入口相连, 中温催化加氢反应器 6加氢产物出口与固液分离装置 7入口相连, 固液分离装置 7固相出口与催化剂再生装置 8 入口相连,催化剂再生装置 8出口与催化剂储槽 9入口相连,催化剂储槽 9出口再与中温催 化加氢反应器 6催化剂入口相连, 固液分离装置 7气相出口与气液分离器 10入口相连。  The intermediate temperature catalytic hydrogenation system II comprises a hydrogen storage tank 4, a hydrogen compressor 5, an intermediate temperature catalytic hydrogenation reactor 6, a solid-liquid separation device 7, a catalyst regeneration device 8, and a catalyst storage tank 9, wherein the hydrogen storage tank 4 outlet Connected to the inlet of the hydrogen compressor 5, the outlet of the hydrogen compressor 5 is connected to the hydrogen inlet of the intermediate temperature catalytic hydrogenation reactor 6, and the outlet of the hydrogenation product of the intermediate temperature catalytic hydrogenation reactor 6 is connected to the inlet of the solid-liquid separation device 7, the solid-liquid separation device 7 The solid phase outlet is connected to the inlet of the catalyst regeneration device 8, the outlet of the catalyst regeneration device 8 is connected to the inlet of the catalyst storage tank 9, and the outlet of the catalyst storage tank 9 is connected to the catalyst inlet of the intermediate temperature catalytic hydrogenation reactor 6, and the gas phase outlet of the solid-liquid separation device 7 is The gas-liquid separator 10 is connected at the inlet.
所述分离与提纯系统 III包括气液分离器 10、抽样检测点 11和混合醇分流装置 12,其中, 气液分离器 10出口与混合醇分流装置 12入口相连, 抽样检测点 11设置在气液分离器 10 出口和混合醇分流装置 12入口之间,混合醇分流装置 12设有回流出口和产物出口,其中回 流出口与酯化反应器 3醇类入口相连。  The separation and purification system III comprises a gas-liquid separator 10, a sampling detection point 11 and a mixed alcohol splitting device 12, wherein the outlet of the gas-liquid separator 10 is connected to the inlet of the mixed alcohol splitting device 12, and the sampling detecting point 11 is set in the gas-liquid Between the separator 10 outlet and the inlet of the mixed alcohol splitting unit 12, the mixed alcohol splitting unit 12 is provided with a reflux outlet and a product outlet, wherein the reflux outlet is connected to the alcoholation reactor 3 alcohol inlet.
利用上述装置, 进行水相生物油制备混合醇类液体燃料的方法, 包括如下步骤: 步骤一、 将水相生物油原料进行酯化, 使水相生物油原料中的有机酸转化为酯类: 将水相生物油储罐 1中的水相生物油原料通过水相生物油泵 2压入酯化反应器 3,水相 生物油原料中的有机酸和通入的醇类发生酯化反应,有机酸被转化为酯类,水相生物油酸度 降低, 稳定性提高, 其中酯化反应器 3工作温度为 150 280 °C, 工作压力为 6~10 MPa; 步骤二、 在中温条件下, 对酯化产物催化加氢:  The method for preparing a mixed alcohol liquid fuel by using the above-mentioned device comprises the following steps: Step 1: esterifying the aqueous phase bio-oil raw material to convert the organic acid in the aqueous phase bio-oil raw material into an ester: The aqueous phase bio-oil raw material in the aqueous bio-oil storage tank 1 is pressed into the esterification reactor 3 through the aqueous bio-oil pump 2, and the organic acid in the aqueous bio-oil raw material is esterified with the introduced alcohol, and organic The acid is converted into an ester, the acidity of the aqueous phase bio-oil is lowered, and the stability is improved, wherein the esterification reactor 3 has an operating temperature of 150 280 ° C and a working pressure of 6 to 10 MPa; Step 2: at a medium temperature, the ester Catalytic hydrogenation of chemical products:
氢气储罐 4中的氢气经氢气压缩机 5加压, 通入中温催化加氢反应器 6, 同时分别加入 步骤一酯化处理后的水相生物油和镍基分子筛催化剂, 在浆态床中经过三相催化加氢反应 后,生成的固液产物通入固液分离装置 7,其中,中温催化加氢反应器 6工作温度为 100 240 °C, 工作压力为 5~8 MPa; 固液分离装置 7分离出固相产物即催化剂, 将催化剂送入催化剂 再生装置 8, 去除催化剂表面积炭, 再生后的催化剂被送入催化剂储槽 9中储存, 再被送入 中温催化加氢反应器 6进行循环使用; 固液分离装置 7分离出液相产物在固液分离装置 7 中被加热蒸发而变成气相产物; The hydrogen in the hydrogen storage tank 4 is pressurized by the hydrogen compressor 5, and is introduced into the intermediate temperature catalytic hydrogenation reactor 6 while being separately added. After the esterification treatment of the aqueous phase bio-oil and the nickel-based molecular sieve catalyst, after the three-phase catalytic hydrogenation reaction in the slurry bed, the solid-liquid product formed is passed into the solid-liquid separation device 7, wherein the medium-temperature catalytic hydrogenation The reactor 6 has an operating temperature of 100 240 ° C and a working pressure of 5 to 8 MPa. The solid-liquid separation device 7 separates the solid phase product, that is, the catalyst, and sends the catalyst to the catalyst regeneration device 8 to remove the catalyst surface area carbon and the regenerated catalyst. It is sent to the catalyst storage tank 9 for storage, and then sent to the intermediate temperature catalytic hydrogenation reactor 6 for recycling; the solid-liquid separation device 7 separates the liquid phase product and is heated and evaporated in the solid-liquid separation device 7 to become a gas phase product. ;
步骤三、 分离提纯得到混合醇类液体燃料:  Step 3: Separating and purifying to obtain a mixed alcohol liquid fuel:
将步骤二生成的气相产物送入气液分离器 10, 经过冷却、 分馏、 提纯, 冷凝后的液相 产物即为混合醇类产物,不冷凝气体为反应产生的尾气和部分未反应的氢气;对混合醇类产 物在抽样检测点 11处取样检测合格后, 将其通入混合醇分流装置 12, 将一部分混合醇类送 入酯化反应器 3中, 作为水相生物油原料酯化处理所需的醇类原料, 进行循环利用; 剩余的 混合醇类即为产品混合醇类液体燃料。  The gas phase product produced in the second step is sent to the gas-liquid separator 10, and after cooling, fractionation and purification, the condensed liquid phase product is a mixed alcohol product, and the non-condensed gas is the tail gas generated by the reaction and a part of unreacted hydrogen; After the mixed alcohol product is sampled and tested at the sampling test point 11, it is passed to the mixed alcohol splitting device 12, and a part of the mixed alcohol is sent to the esterification reactor 3 as an aqueous phase bio-oil raw material esterification treatment station. The required alcohol raw materials are recycled; the remaining mixed alcohols are the product mixed alcohol liquid fuels.
实施例采用的水相生物油原料来自山东某公司,其含有的组分百分比如下:醇类占 3%、 酯类占 3%、 醚类占 4%、 酮类占 16%、 酚类占 12%、 酸类占 38%、 醛类占 11%、 其他组分 占 13%。  The aqueous phase bio-oil raw materials used in the examples are from a company in Shandong, which contains the following percentages: alcohols 3%, esters 3%, ethers 4%, ketones 16%, and phenols 12 %, acid accounted for 38%, aldehydes accounted for 11%, and other components accounted for 13%.
实施例 1  Example 1
利用图 1所示装置进行水相生物油制备混合醇类液体燃料的方法, 包括如下步骤: 步骤一、 将水相生物油原料进行酯化, 使水相生物油原料中的有机酸转化为酯类: 将水相生物油储罐 1中 40 g水相生物油原料通过水相生物油泵 2压入酯化反应器 3,首 先没有制备得到混合醇的情况下采用甲醇和水相生物油按质量比为 3: 1进料混合,保持反应 温度为 240 V, 压力为 8 MPa, 水相生物油中的有机酸和醇类发生酯化反应, 反应完全, 有机酸被转化为酯类, 水相生物油酸度降低, 稳定性有所提高。  The method for preparing a mixed alcohol liquid fuel by using the apparatus shown in Fig. 1 comprises the following steps: Step 1: esterifying the aqueous phase bio-oil raw material to convert the organic acid in the aqueous phase bio-oil raw material into an ester Class: 40 g of aqueous bio-oil raw material in the aqueous bio-oil storage tank 1 is pressed into the esterification reactor 3 through the aqueous bio-oil pump 2, firstly using methanol and aqueous bio-oil according to the quality without preparing the mixed alcohol. The ratio is 3: 1 feed mixing, maintaining the reaction temperature is 240 V, the pressure is 8 MPa, the organic acid and alcohol in the aqueous bio-oil are esterified, the reaction is complete, the organic acid is converted into ester, water phase Bio-oil has reduced acidity and improved stability.
步骤二、 利用浆态床在中温条件下, 对酯化产物催化加氢:  Step 2: catalytic hydrogenation of the esterification product by using a slurry bed at a medium temperature condition:
氢气储罐 4中的 60 mL氢气经氢气压缩机 5加压, 通入中温催化加氢反应器 6, 同时分 别加入步骤一酯化处理后的水相生物油和 2 g镍基分子筛催化剂 M-HZSM-5,保持反应温度 为 140 V, 压力为 6 MPa, 反应完全; 经过三相催化加氢反应后, 生成的固液产物即加氢 产物通入固液分离装置 7, 其中, 三相指固相: 催化剂, 液相: 酯化水相生物油, 气相: 氢 气; 固液分离装置 (挥发器) 12 分离出固相产物即催化剂; 然后将催化剂送入催化剂再生 装置 8, 去除催化剂表面积炭, 再生后的催化剂被送入催化剂储槽 8中储存, 最后再被送入 中温催化加氢反应器 6, 进行循环使用, 液相产物在固液分离装置(挥发器) 12中被加热蒸 发而变成气相产物。 60 mL of hydrogen in the hydrogen storage tank 4 is pressurized by the hydrogen compressor 5, and is introduced into the intermediate temperature catalytic hydrogenation reactor 6, and simultaneously added the aqueous phase bio-oil and the 2 g nickel-based molecular sieve catalyst M-step after the esterification treatment. HZSM-5, maintaining a reaction temperature of 140 V and a pressure of 6 MPa, the reaction is complete; after three-phase catalytic hydrogenation reaction, the solid-liquid product, that is, the hydrogenated product, is introduced into the solid-liquid separation device 7, wherein the three-phase finger Solid phase: catalyst, liquid phase: esterified aqueous bio-oil, gas phase: hydrogen; solid-liquid separation device (volatiles) 12 Separation of solid phase product, ie catalyst; then catalyst is sent to catalyst regeneration unit 8, to remove catalyst surface area carbon The regenerated catalyst is sent to the catalyst storage tank 8 for storage and finally sent The intermediate temperature catalytic hydrogenation reactor 6 is recycled, and the liquid phase product is heated and evaporated in a solid-liquid separation device (volatiles) 12 to become a gas phase product.
步骤三、 分离提纯得到混合醇类液体燃料:  Step 3: Separating and purifying to obtain a mixed alcohol liquid fuel:
将步骤二生成的气相产物送入气液分离器 10, 经过冷却、 分馏、 提纯, 冷凝后的液相 产物即为混合醇类产物,不冷凝气体为反应产生的尾气和部分未反应的氢气;对混合醇类产 物在抽样检测点 11处取样检测合格后, 将其通入混合醇分流装置 12, 将一部分混合醇类送 入酯化反应器 3中, 作为酯化处理水相生物油所需的醇类原料, 进行循环利用, 剩余的产品 作为混合醇类液体燃料。  The gas phase product produced in the second step is sent to the gas-liquid separator 10, and after cooling, fractionation and purification, the condensed liquid phase product is a mixed alcohol product, and the non-condensed gas is the tail gas generated by the reaction and a part of unreacted hydrogen; After the mixed alcohol product is sampled and tested at the sampling test point 11, it is passed to the mixed alcohol splitting device 12, and a part of the mixed alcohol is sent to the esterification reactor 3 as required for esterification of the aqueous phase bio-oil. The alcohol raw material is recycled, and the remaining product is used as a mixed alcohol liquid fuel.
本实例中采用以上方法对水相生物油原料进行酯化加氢, 情况如下: 醇类占 3%、 酯类 占 3%、醚类占 4%、酮类占 16%、酚类占 12%、酸类占 38%、醛类占 11%、其他组分占 13%; 经酯化后醇类占 64%、 酯类占 21%、 醚类占 3%、 酮类占 4%、 酚类占 6%、 酸类占 2%; 再 经过催化加氢后醇类占 82%、 酯类占 16%、 醚类占 2%, 实现了酸类化合物的全部转化。 实施例 2  In the present example, the above method was used to carry out esterification and hydrogenation of aqueous bio-oil raw materials, as follows: alcohols accounted for 3%, esters accounted for 3%, ethers accounted for 4%, ketones accounted for 16%, and phenols accounted for 12%. Acids accounted for 38%, aldehydes accounted for 11%, other components accounted for 13%; after esterification, alcohols accounted for 64%, esters accounted for 21%, ethers accounted for 3%, ketones accounted for 4%, phenols 6%, acid accounted for 2%; after catalytic hydrogenation, alcohol accounted for 82%, esters accounted for 16%, ethers accounted for 2%, achieving the full conversion of acid compounds. Example 2
本实施例与实施例 1的不同点在于, 步骤一反应温度为 150 V, 压力为 6 MPa; 步骤 二反应温度为 100 V, 压力为 5 MPa。 The difference between this embodiment and Example 1 is that the reaction temperature of step 1 is 150 V and the pressure is 6 MPa ; the reaction temperature of step 2 is 100 V, and the pressure is 5 MPa.
本实例中采用以上方法对水相生物油原料进行酯化加氢,情况如下:水相生物油原料中 各组分的质量分数如下: 醇类占 3%、 酯类占 3%、 醚类占 4%、 酮类占 16%、 酚类占 12%、 酸类占 38%、 醛类占 11%、 其他组分占 13%; 经酯化后醇类占 47%、 酯类占 18%、 醚类占 3%、 酮类占 8%、 酚类占 7%、 醛类占 5%、 酸类占 12%; 再经过催化加氢后醇类占 62%、 酯类占 14%、 醚类占 3%, 酮类占 4%、 酚类占 5%、 醛类占 5%、 酸类占 7%。  In the present example, the above method is used to carry out esterification and hydrogenation of the aqueous phase bio-oil raw materials, as follows: the mass fraction of each component in the aqueous bio-oil raw material is as follows: alcohol accounts for 3%, ester accounts for 3%, and ether accounts for 4%, ketones accounted for 16%, phenols accounted for 12%, acids accounted for 38%, aldehydes accounted for 11%, other components accounted for 13%; after esterification, alcohol accounted for 47%, esters accounted for 18%, Ethers accounted for 3%, ketones accounted for 8%, phenols accounted for 7%, aldehydes accounted for 5%, acids accounted for 12%; after catalytic hydrogenation, alcohols accounted for 62%, esters accounted for 14%, ethers 3%, ketones accounted for 4%, phenols accounted for 5%, aldehydes accounted for 5%, and acids accounted for 7%.
实施例 3  Example 3
本实施例与实施例 1的不同点在于, 步骤一反应温度为 280 °C, 压力为 lO MPa; 步骤 二反应温度为 240 V, 压力为 8 MPa。  The difference between this embodiment and Example 1 is that the reaction temperature in step 1 is 280 ° C and the pressure is 10 MPa; the reaction temperature in step 2 is 240 V and the pressure is 8 MPa.
本实例中采用以上方法对水相生物油原料进行酯化加氢,情况如下:水相生物油原料中 各组分的质量分数如下: 醇类占 3%、 酯类占 3%、 醚类占 4%、 酮类占 16%、 酚类占 12%、 酸类占 38%、 醛类占 11%、 其他组分占 13%; 经酯化后醇类占 71%、 酯类占 17%、 醚类占 2%、 酮类占 3%、 酚类占 6%、 酸类占 1%; 再经过催化加氢后醇类占 86%、 酯类占 13%、 醚类占 1%, 实现了酸类化合物的全部转化。 以上所述仅为本发明的较佳实施方式,本发明的保护范围并不以上述实施方式为限,但 凡本领域普通技术人员根据本发明所揭示内容所作的等效修饰或变化,皆应纳入权利要求书 中记载的保护范围内。 In the present example, the above method is used to carry out esterification and hydrogenation of the aqueous phase bio-oil raw materials, as follows: the mass fraction of each component in the aqueous bio-oil raw material is as follows: alcohol accounts for 3%, ester accounts for 3%, and ether accounts for 4%, ketones accounted for 16%, phenols accounted for 12%, acids accounted for 38%, aldehydes accounted for 11%, other components accounted for 13%; after esterification, alcohol accounted for 71%, esters accounted for 17%, Ethers accounted for 2%, ketones accounted for 3%, phenols accounted for 6%, and acids accounted for 1%. After catalytic hydrogenation, alcohols accounted for 86%, esters accounted for 13%, and ethers accounted for 1%. Total conversion of acid compounds. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, but equivalent modifications or variations made by those skilled in the art according to the disclosure of the present invention should be incorporated. Within the scope of protection stated in the claims.

Claims

权利要求书 Claim
1、 一种水相生物油制备混合醇类液体燃料的装置, 其特征在于, 它包括水相生物油酯 化系统 ( I )、 中温催化加氢系统 (Π) 和分离与提纯系统 (III); 1. A device for preparing a mixed alcohol liquid fuel by using an aqueous phase bio-oil, characterized in that it comprises an aqueous phase bio-oil esterification system (I), a medium-temperature catalytic hydrogenation system (Π), and a separation and purification system (III) ;
所述水相生物油酯化系统 ( I ) 包括水相生物油储罐 (1)、 水相生物油泵 (2) 和酯化 反应器 (3), 其中, 水相生物油储罐 (1) 出口与水相生物油泵 (2) 入口相连, 水相生物油 泵 (2) 出口与酯化反应器 (3) 水相生物油入口相连, 酯化反应器 (3) 出口与中温催化加 氢反应器 (6) 酯化产物入口相连;  The aqueous bio-oil esterification system (I) comprises an aqueous bio-oil storage tank (1), an aqueous bio-oil pump (2) and an esterification reactor (3), wherein the aqueous bio-oil storage tank (1) The outlet is connected to the inlet of the aqueous bio-oil pump (2), the aqueous bio-oil pump (2) is connected to the esterification reactor (3), the aqueous bio-oil inlet is connected, the esterification reactor (3) is outlet and the intermediate-temperature catalytic hydrogenation reactor (6) the esterification product inlets are connected;
所述中温催化加氢系统 (Π) 包括氢气储罐 (4)、 氢气压缩机 (5)、 中温催化加氢反应 器 (6)、 固液分离装置 (7)、 催化剂再生装置 (8) 和催化剂储槽 (9), 其中, 氢气储罐 The medium temperature catalytic hydrogenation system (Π) includes a hydrogen storage tank (4), a hydrogen compressor (5), a medium temperature catalytic hydrogenation reactor (6), a solid-liquid separation device (7), a catalyst regeneration device (8), and Catalyst storage tank (9), wherein hydrogen storage tank
(4) 出口与氢气压缩机 (5) 入口相连, 氢气压缩机 (5) 出口与中温催化加氢反应器 (6) 氢气入口相连, 中温催化加氢反应器 (6) 加氢产物出口与固液分离装置 (7) 入口相连, 固 液分离装置 (7) 固相出口与催化剂再生装置 (8) 入口相连, 催化剂再生装置 (8) 出口与 催化剂储槽 (9) 入口相连, 催化剂储槽 (9) 出口再与中温催化加氢反应器 (6) 催化剂入 口相连, 固液分离装置 (7) 气相出口与气液分离器 (10) 入口相连; (4) The outlet is connected to the inlet of the hydrogen compressor (5), the outlet of the hydrogen compressor (5) is connected to the intermediate temperature catalytic hydrogenation reactor (6), the hydrogen inlet is connected, and the intermediate temperature catalytic hydrogenation reactor (6) is the hydrogenation product outlet and solid. The liquid separation device (7) is connected to the inlet, the solid-liquid separation device (7) is connected to the inlet of the catalyst regeneration device (8), and the outlet of the catalyst regeneration device (8) is connected to the inlet of the catalyst storage tank (9), the catalyst storage tank ( 9) the outlet is connected to the catalyst inlet of the intermediate temperature catalytic hydrogenation reactor (6), and the gas phase outlet of the solid-liquid separation device (7) is connected to the inlet of the gas-liquid separator (10);
所述分离与提纯系统 (III) 包括气液分离器 (10)、 抽样检测点 (11) 和混合醇分流装 置 (12), 其中, 气液分离器 (10) 出口与混合醇分流装置 (12) 入口相连, 抽样检测点 The separation and purification system (III) comprises a gas-liquid separator (10), a sampling detection point (11) and a mixed alcohol splitting device (12), wherein the gas-liquid separator (10) outlet and the mixed alcohol splitting device (12) ) entrance connected, sampling checkpoint
(11) 设置在气液分离器 (10) 出口和混合醇分流装置 (12) 入口之间, 混合醇分流装置(11) Between the gas-liquid separator (10) outlet and the inlet of the mixed alcohol splitter (12), the mixed alcohol splitter
(12) 设有回流出口和产物出口, 混合醇分流装置 (12) 回流出口与酯化反应器 (3) 醇类 入口相连。 (12) There is a reflux outlet and a product outlet, and the mixed alcohol splitting device (12) is connected to the esterification reactor (3) alcohol inlet.
2、 利用权利要求 1 所述的装置进行水相生物油制备混合醇类液体燃料的方法, 其特征 在于, 它包括以下步骤:  2. A method of preparing a mixed alcoholic liquid fuel using aqueous phase bio-oil using the apparatus of claim 1, characterized in that it comprises the steps of:
步骤一、 将水相生物油原料进行酯化, 使水相生物油原料中的有机酸转化为酯类: 将水相生物油储罐 (1) 中的水相生物油原料通过水相生物油泵 (2) 压入酯化反应器 (3), 水相生物油原料中的有机酸和通入的醇类发生酯化反应, 有机酸被转化为酯类, 得到 酯化水相生物油;  Step 1: The aqueous phase bio-oil raw material is esterified to convert the organic acid in the aqueous bio-oil raw material into an ester: the aqueous bio-oil raw material in the aqueous bio-oil storage tank (1) is passed through the aqueous bio-oil pump (2) pressing into the esterification reactor (3), the organic acid in the aqueous phase bio-oil raw material is esterified with the introduced alcohol, and the organic acid is converted into an ester to obtain an esterified aqueous phase bio-oil;
步骤二、 在中温条件下, 对酯化产物催化加氢:  Step 2. Catalytic hydrogenation of the esterification product under moderate temperature conditions:
氢气储罐 (4) 中的氢气经氢气压缩机 (5) 加压, 通入中温催化加氢反应器 (6), 同时 分别加入步骤一得到的酯化水相生物油和催化剂, 经过三相催化加氢反应后, 生成的固液产 物通入固液分离装置 (7); 固液分离装置 (7) 分离出固相产物即催化剂, 将催化剂送入催 化剂再生装置 (8 ), 去除催化剂表面积炭, 再生后的催化剂被送入催化剂储槽 (9 ) 中储 存, 再被送入中温催化加氢反应器 (6) 进行循环使用; 固液分离装置 (7) 分离出液相产物 在固液分离装置 (7) 中被加热蒸发而变成气相产物; The hydrogen in the hydrogen storage tank (4) is pressurized by the hydrogen compressor (5), and is introduced into the intermediate temperature catalytic hydrogenation reactor (6), and the esterified aqueous phase bio-oil and catalyst obtained in the first step are respectively added, and the three-phase is passed. After the catalytic hydrogenation reaction, the solid-liquid product formed is introduced into the solid-liquid separation device (7); the solid-liquid separation device (7) separates the solid phase product, that is, the catalyst, and the catalyst is sent to the catalyst. a chemical regeneration device (8) for removing catalyst surface area carbon, and the regenerated catalyst is sent to a catalyst storage tank (9) for storage, and then sent to an intermediate temperature catalytic hydrogenation reactor (6) for recycling; solid-liquid separation device (7) separating the liquid phase product by heating and evaporating in the solid-liquid separation device (7) to become a gas phase product;
步骤三、 分离提纯得到混合醇类液体燃料:  Step 3: Separating and purifying to obtain a mixed alcohol liquid fuel:
将步骤二生成的气相产物送入气液分离器 (10), 经过冷却、 分馏、 提纯, 冷凝后的液 相产物即为混合醇类产物, 不冷凝气体为反应产生的尾气和部分未反应的氢气; 对混合醇类 产物在抽样检测点 (11 ) 处取样检测合格后, 将其通入混合醇分流装置 (12), 将一部分混 合醇类送入酯化反应器 (3 ) 中, 作为水相生物油原料酯化处理所需的醇类原料, 进行循环 利用; 剩余的为产品混合醇类液体燃料。  The gas phase product produced in the second step is sent to the gas-liquid separator (10), and after cooling, fractionation and purification, the condensed liquid phase product is a mixed alcohol product, and the non-condensed gas is the tail gas generated by the reaction and partially unreacted. Hydrogen; after sampling and testing the mixed alcohol product at the sampling test point (11), it is passed to the mixed alcohol splitting device (12), and a part of the mixed alcohol is sent to the esterification reactor (3) as water. The alcohol raw material required for the esterification treatment of the phase bio-oil feedstock is recycled; the remainder is the product mixed alcoholic liquid fuel.
3、 根据权利要求 2 所述水相生物油制备混合醇类燃料的方法, 其特征在于, 步骤一 中, 所述酯化反应器 (3 ) 工作温度为 150 280 V, 工作压力为 6~10 MPa。  3. The method for preparing a mixed alcohol fuel according to claim 2, wherein in the first step, the esterification reactor (3) has an operating temperature of 150 280 V and a working pressure of 6-10. MPa.
4、 根据权利要求 2 所述水相生物油制备混合醇类燃料的方法, 其特征在于, 步骤二 中, 所述中温催化加氢反应器 (6) 工作温度为 100 240 V, 工作压力为 5~8 MPa。  The method for preparing a mixed alcohol fuel according to claim 2, wherein in the second step, the medium temperature catalytic hydrogenation reactor (6) has an operating temperature of 100 240 V and a working pressure of 5 ~8 MPa.
5、 根据权利要求 2或 4所述水相生物油制备混合醇类燃料的方法, 其特征在于, 步骤 二中, 所述三相催化加氢反应在浆态床中反应。  The method for preparing a mixed alcohol fuel according to claim 2 or 4, wherein in the second step, the three-phase catalytic hydrogenation reaction is carried out in a slurry bed.
6、 根据权利要求 5 所述水相生物油制备混合醇类燃料的方法, 其特征在于, 步骤二 中, 所述催化剂为镍基分子筛。  6. A method of preparing a mixed alcohol fuel according to claim 5, wherein in the second step, the catalyst is a nickel-based molecular sieve.
PCT/CN2014/080907 2013-09-04 2014-06-27 Method and apparatus for preparing mixed alcohol liquid fuel from aqueous phase bio-oil WO2015032237A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643666A (en) * 2009-08-24 2010-02-10 中国科学技术大学 Method for refining biological oil by homogeneous catalysis
WO2012000033A1 (en) * 2010-07-01 2012-01-05 Ignite Energy Resources Limited Ballistic heating process
CN102653691A (en) * 2012-02-29 2012-09-05 东南大学 Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil
CN202543163U (en) * 2012-02-29 2012-11-21 东南大学 Device for preparing oxygen-containing liquid fuel by performing catalytic conversion on bio oil
CN102925293A (en) * 2012-10-10 2013-02-13 上海交通大学 Method for preparing high-quality esterification bio-oil by catalytic esterification reaction
CN103436305A (en) * 2013-09-04 2013-12-11 东南大学 Method and device for preparing alcohol mixed liquid fuel from aqueous-phase biological oil

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8518576D0 (en) * 1985-07-23 1985-08-29 Bp Chem Int Ltd Hydrogenation of carboxylic acid esters to alcohols
US5120885A (en) * 1990-09-21 1992-06-09 Kao Corporation Process for producing alcohol
JPH0699337B2 (en) * 1990-12-27 1994-12-07 花王株式会社 Alcohol production method
JP2003321683A (en) * 2002-04-30 2003-11-14 Frontier Japan:Kk Method for producing fuel for engine, apparatus for production and plant for production
CN1974510B (en) * 2006-12-12 2011-06-08 四川大学 Process for hydrogenating carboxylic acid and its ester to prepare alcohol

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643666A (en) * 2009-08-24 2010-02-10 中国科学技术大学 Method for refining biological oil by homogeneous catalysis
WO2012000033A1 (en) * 2010-07-01 2012-01-05 Ignite Energy Resources Limited Ballistic heating process
CN102653691A (en) * 2012-02-29 2012-09-05 东南大学 Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil
CN202543163U (en) * 2012-02-29 2012-11-21 东南大学 Device for preparing oxygen-containing liquid fuel by performing catalytic conversion on bio oil
CN102925293A (en) * 2012-10-10 2013-02-13 上海交通大学 Method for preparing high-quality esterification bio-oil by catalytic esterification reaction
CN103436305A (en) * 2013-09-04 2013-12-11 东南大学 Method and device for preparing alcohol mixed liquid fuel from aqueous-phase biological oil

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