WO2011035571A1 - 一种木质纤维素类生物质水解重整制备生物汽油的方法 - Google Patents

一种木质纤维素类生物质水解重整制备生物汽油的方法 Download PDF

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WO2011035571A1
WO2011035571A1 PCT/CN2010/071310 CN2010071310W WO2011035571A1 WO 2011035571 A1 WO2011035571 A1 WO 2011035571A1 CN 2010071310 W CN2010071310 W CN 2010071310W WO 2011035571 A1 WO2011035571 A1 WO 2011035571A1
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Prior art keywords
hydrolyzed
reforming
liquid
temperature
mpa
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PCT/CN2010/071310
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English (en)
French (fr)
Inventor
马隆龙
王铁军
袁振宏
张兴华
庄新姝
吴创之
江婷
章青
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中国科学院广州能源研究所
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Priority to US13/497,939 priority Critical patent/US8562697B2/en
Priority to DK10818265.0T priority patent/DK2487224T3/en
Priority to EP10818265.0A priority patent/EP2487224B1/en
Publication of WO2011035571A1 publication Critical patent/WO2011035571A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to the field of biomass energy chemical technology, and in particular to a method for preparing biogasoline by hydrolyzing reforming lignocellulose-based biomass. Background technique
  • Lignocellulosic biomass including agricultural waste and residues, forestry and forestry processing waste, grass, etc.
  • main organic components include cellulose, hemicellulose and wood.
  • the cellulose is hydrolyzed to form glucose
  • the hemicellulose is hydrolyzed to form xylose, arabinose, galactose and the like.
  • Hydrolysis is one of the key steps in the development and utilization of biomass resources such as lignocellulose.
  • High-temperature liquid water generally refers to compressed liquid water at a temperature between 180 and 350 ° C. It has not only acid-catalyzed and alkali-catalyzed functions, but also has the property of simultaneously dissolving organic and inorganic substances. Due to its fast reaction rate, good solubility, self-acid catalysis and alkali catalysis, selective decomposition, and inhibition of coking caused by thermal decomposition, it has attracted widespread attention.
  • the use of high-temperature liquid water to hydrolyze biomass resources to produce chemical raw materials has the advantages of no catalyst recovery, water recycling, and less pollution, and has shown a very broad application prospect in the field of biomass resources.
  • Acid hydrolysis can directly hydrolyze lignocellulosic biomass to produce monosaccharides, which has good operability and economic feasibility.
  • Ultra-low acid hydrolysis is a novel process for the hydrolysis of biomass acid. Hydrolysis of biomass into monosaccharides and oligosaccharides is carried out by using an acid having a concentration of less than 0.1% (usually using a strong acid such as sulfuric acid or hydrochloric acid) as a catalyst. However, in the acidic medium, the monosaccharide is easily degraded, and a substance having a certain side effect on the subsequent aqueous phase catalytic reforming reaction such as furfural and HMF (which is easy to polymerize and deactivate the catalyst) is formed. Therefore, it is generally necessary to moderately detoxify the dilute acid hydrolyzate.
  • Aqueous phase catalytic reforming is a novel process for preparing liquid helium hydrocarbons by catalyzing the composition of lignocellulosic hydrolysate.
  • the reaction conditions of the process are relatively mild. It has been reported that under the action of a noble metal catalyst such as Pt, the conversion rate of monosaccharides in the aqueous phase can reach 85 wt.% or more at 200 to 300 ° C and a pressure of about 2 MPa.
  • the product of aqueous phase reforming is bio-gasoline with C 5 and C 6 alkane as main components, which can be added to motor gasoline in a high proportion. It is more energy-efficient than traditional ethanol gasoline and is suitable for any ordinary car or ethanol gasoline car.
  • the aqueous phase catalytic reforming mainly adopts a process with a system with a relatively complicated four-phase catalytic reactor as the core, and the process conditions are complicated; and the precious metal catalyst used is expensive and economically unbearable; and the catalyst is easy to accumulate carbon loss. Live, shortcomings of short service life. Summary of the invention
  • the object of the present invention is to overcome the deficiencies in the prior art and to provide a novel process for preparing biogasoline by hydrolyzing catalytic reforming using lignocellulosic biomass as a raw material.
  • a method for preparing biogasoline by hydrolyzing and reforming lignocellulosic biomass comprises the following steps:
  • the hydrolyzed raw material liquid enters a low temperature reforming reactor filled with a Ni/Al 2 0 3 -SiO 2 catalyst, and the reaction is carried out under the conditions of 160-210 ° C and a hydrogen pressure of 4.0 to 6.5 MPa;
  • the reactant from the low-temperature reforming reactor enters a high-temperature reforming reactor filled with a Ni/HZSM-5 catalyst, and the reaction is carried out at 210 to 270 ° C under a hydrogen pressure of 2.0 to 5.6 MPa;
  • the reactants from the high-temperature reforming reactor are condensed and then subjected to gas-liquid separation.
  • the uncondensed biogasoline is decompressed and then absorbed by the absorbing liquid C 6 ⁇ hydrocarbon; the liquid is phase separated by a phase separator, and the phase is separated.
  • the upper layer of the device gets biogasoline.
  • the hydrolyzed raw material liquid of the step (1) is obtained by the following steps:
  • Lignocellulosic biomass is hydrolyzed in a high temperature liquid aqueous medium with a pressure of 2.0-5.0 MPa 40 ⁇
  • the filtrate is a high temperature liquid water hydrolyzate
  • Step a) The filtered residue is hydrolyzed in a maleic acid solution at 160-220 ° C, 2.0-5.0 MPa, 0.01-0.1% by mass, and the filtrate is a maleic acid hydrolyzate;
  • step c) mixing the high temperature liquid water hydrolyzate of step a) with the maleic acid hydrolyzate of step b) to obtain a hydrolyzed raw material Liquid.
  • the temperature of the high temperature liquid water is 180 to 200 ° C, and in this temperature range, the hemicellulose in the biomass can be hydrolyzed at a faster rate without excessive hydrolysis;
  • the ultra-low maleic acid has a mass percent concentration of 0.06-0.08%, and within this concentration range, the cellulose in the biomass is efficiently hydrolyzed without excessive hydrolysis.
  • the reaction condition of the step (2) is 190 to 200 ° C, and the hydrogen pressure is 5.0 MPa.
  • the reaction condition of the step (3) is 240 to 250 ° C, and the hydrogen pressure is 4.0 MPa.
  • the invention utilizes a low-cost nickel-based catalyst to directly prepare a bio-gasoline by directly treating a hydrolyzed raw material liquid by a two-stage aqueous phase catalytic reforming process, and the process is simple, and some active organic substances are hydroconverted in a low temperature section, thereby avoiding high temperature.
  • the segment polymerizes coke deposits, thereby avoiding unfavorable factors such as easy carbon deposition and deactivation of the catalyst; and the product can be automatically separated and separated, thereby avoiding processes such as rectification and purification of the product.
  • the invention prepares bio-gasoline from lignocellulosic biomass as raw material, and the raw material source is wide and low.
  • the product can be directly utilized in the existing vehicle engine system, and has a good market prospect, and a biomass is prepared as a raw material.
  • the invention uses high-temperature liquid water and ultra-low weak acid-maleic acid to hydrolyze biomass to thoroughly hydrolyze the biomass, and the acidity of the maleic acid is very low, which reduces the corrosiveness of the equipment.
  • the hydrolyzed feedstock does not need to be detoxified and directly enters the catalytic reforming system for aqueous phase catalytic reforming to prepare biogasoline.
  • FIG. 1 is a schematic view showing the working process of preparing a bio-gasoline by aqueous phase catalytic reforming of a hydrolyzed raw material liquid according to the present invention
  • reference numerals 1. a hydrolyzate storage tank; 2. a metering injection pump; 3. a low temperature reforming reactor; Reforming reactor; 5, condenser; 6, gas-liquid separator; 7, absorption tank; 8, phase separator; 9, hydrogen flow meter; 10, liquid level control solenoid valve.
  • Examples 1-3 are a method for preparing a hydrolyzed raw material liquid by high temperature liquid water-ultra-low maleic acid combined hydrolysis.
  • Example 1 is a method for preparing a hydrolyzed raw material liquid by high temperature liquid water-ultra-low maleic acid combined hydrolysis.
  • the preparation method of the hydrolysis raw material liquid comprises the following steps:
  • Example 1 60.6 8.19
  • Example 2 53.8 9.69
  • Example 3 39.7 7.11
  • Example 4-6 An aqueous phase catalytic reforming reaction was carried out using the hydrolyzed raw material liquid obtained in Example 2 as a raw material.
  • Example 4 An aqueous phase catalytic reforming reaction was carried out using the hydrolyzed raw material liquid obtained in Example 2 as a raw material.
  • the method for preparing bio-gasoline by aqueous phase catalytic reforming of a hydrolyzed raw material liquid comprises the following steps:
  • the hydrolyzed raw material liquid is fed from the bottom of the low-temperature reforming reactor 3 into the low-temperature reforming reactor 3 filled with the Ni/Al 2 0 3 -SiO 2 catalyst by the metering injection pump 2, and is entrained into the catalyst bed by the H 2 gas stream. Carry out the reaction.
  • the reaction temperature was 190 ° C and the hydrogen pressure was 5.0 MPa.
  • the reactant from the low-temperature reforming reactor 3 is directly passed from the bottom of the high-temperature reforming reactor 4 into the high-temperature reforming reactor 4 filled with the Ni/HZSM-5 catalyst under the pressure difference, and is entrained by the H 2 gas stream. Enter the catalyst bed to carry out the reaction.
  • the reaction temperature was 240 ° C and the hydrogen pressure was 4.0 MPa.
  • a method for preparing bio-gasoline by catalytic reforming of a hydrolyzed raw material liquid wherein the reaction temperature of the low-temperature catalytic reactor is 210 ° C, the pressure is 6.5 MPa, the catalytic temperature of the high-temperature catalytic reactor is 270 V, and the pressure is 5.6 MPa, and the remaining operation modes,
  • the reaction conditions were the same as in Example 4.
  • the total carbon conversion rate in the hydrolyzed raw material liquid of Example 4-6 and the distribution of the product after the catalytic reaction were measured, and the results are shown in Table 2.
  • the results in Table 2 indicate that the hydrolysis feedstock solution has a reaction temperature of 190 ° C and a pressure of 5.0 MPa in a low-temperature catalytic reactor, a high-temperature catalytic reactor reaction temperature of 240 ° C, and a pressure of 4.0 MPa (ie, Example 4).
  • the reaction conditions have the highest carbon conversion rate, and the content of C 5 , C 6 and C 7 in the product amounts to 74.9% (mol %).
  • the carbon conversion rate and product in the hydrolyzate The selectivity of C 5 and C 6 , 0 7 reached a good combination, and the yield of biogasoline was the highest under this process condition.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Processing Of Solid Wastes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本发明公开一种以木质纤维素类生物质为原料水解重整制备生物汽油的方法。该方法采用将水解木质纤维素类生物质后的得到的水解原料液直接进入水相催化重整系统，依次在填充有催化剂Ni/SiO2-Al2O3的低温重整反应器和填充有Ni/HZSM-5的高温重整催化器中进行水相催化重整反应，反应物经冷凝后进行气液分离，未冷凝的生物汽油减压后由吸收液C6烷烃吸收；液体经相分离器进行相分离， 在相分离器的上层得到生物汽油。 本发明开辟了一条以生物质为原料制备高品位液体燃料油的新方法， 该方法能自动分层分离， 避免了产品精馏提纯等工艺， 原料来源广泛而低廉， 产品可直接利用于现有的车载发动机系统， 具有良好的市场前景。

Description

一种木质纤维素类生物质水解重整制备生物汽油的方法 技术领域
本发明涉及生物质能化工技术领域，具体的说，本发明涉及一种木质纤维素 类生物质水解重整制备生物汽油的方法。 背景技术
木质纤维素类生物质包括农业生产的废弃物和剩余物、林木及林业加工废弃 物、 草类等， 是地球上最丰富的可再生资源， 其主要有机成分包括纤维素、 半纤 维素和木质素三部分。纤维素经水解可生成葡萄糖，半纤维素经水解可生成木糖、 阿拉伯糖、半乳糖等。水解是木质纤维素等生物质资源开发利用的关键歩骤之一。
高温液态水通常是指温度在 180~350°C之间的压缩液态水， 它不仅具有酸催 化与碱催化的功能，而且具有能同时溶解有机物与无机物的特性。 由于具有反应 速度快、溶解性能良好、 自身具有酸催化和碱催化功能、 可实现选择性分解、 能 抑制由热分解产生的焦化等特性， 引起了广泛的关注。利用高温液态水的特性水 解生物质资源生产化工原料，具有无催化剂回收、水可循环利用、污染少等优点， 在生物质资源领域显示出非常广阔的应用前景。
酸水解可以直接将木质纤维素类生物质水解产生单糖，具有较好的可操作性 和经济可行性。超低酸水解是生物质酸水解的一种新型工艺，是以浓度低于 0.1% 的酸 (一般采用硫酸、 盐酸等强酸)为催化剂， 对生物质水解成单糖和低聚糖。 但 是在酸性介质中单糖很容易发生降解， 生成糠醛以及 HMF等对后续水相催化重 整反应有一定的副作用的物质 (容易聚合， 使催化剂失活)。 因此， 一般需要对稀 酸水解液进行适度地脱毒处理。
水相催化重整是催化木质纤维素水解液成分制备液体垸烃的新型工艺。该工 艺反应条件比较温和， 曾报道在 Pt等贵金属催化剂作用下， 200〜300°C、 压力 2MPa左右， 水相中的单糖转化率可达 85wt.%以上。 水相重整的产物是以 C5、 C6 烷烃为主要成分的生物汽油，可以高比例地加入到车用汽油中， 比传统的乙醇汽 油能效更高，适用于任何普通汽车或乙醇汽油汽车， 并且不需要为此更改汽车发 动机的设计和制造专门的汽油调和设备。不仅如此，水相重整水解液中的碳水化 合物还具有潜在的优势： 热效率高。 反应均在液相中进行， 避免了原料的气化； 反应产物垸烃可以与水相自动分离， 避免了蒸馏等耗能过程， 据估计， 该过程的 热效率大约是碳水化合物发酵制乙醇的 2倍； 为此， 2006年， Science曾发表专栏 评论，高度评价该过程为农林废弃物的利用提供了一条新的途径- 从生物质到汽 油，实现基础化学品来源于可再生资源，为经济有序地可持续发展转变创造机会, 所以引起了学界、 工商界的高度关注。
但是目前水相催化重整主要采用以系统相当复杂的四相催化反应器为核心 的工艺， 工艺条件很复杂； 而且使用的贵金属催化剂价格高昂， 在经济上难以承 受； 且存在催化剂容易积碳失活， 使用寿命不长的缺点。 发明内容
本发明的目的在于克服现有技术中的缺陷，提供一种以木质纤维素类生物质 为原料水解催化重整制备生物汽油的新工艺。
为了实现上述目的， 本发明釆取了以下技术方案：
一种木质纤维素类生物质水解重整制备生物汽油的方法， 包括以下歩骤：
(1)水解木质纤维素类生物质得到水解原料液；
(2)水解原料液进入填充有 Ni/Al203-Si02催化剂的低温重整反应器， 160- 210°C， 氢气压力 4.0〜6.5MPa条件下进行反应；
(3)从低温重整反应器出来的反应物进入填充有 Ni/HZSM-5催化剂的高温重 整反应器， 210〜270°C， 氢气压力为 2.0〜5.6MPa条件下进行反应；
(4)从高温重整反应器出来后的反应物冷凝后进行气液分离， 未冷凝的生物 汽油减压后由吸收液 C6垸烃吸收； 液体经相分离器进行相分离， 在相分 离器的上层得到生物汽油。
所述步骤 (1)的水解原料液是通过以下步骤得到的：
a) 木质纤维素类生物质在压力为 2.0-5.0MPa的高温液态水介质中水解 40〜
90min后过滤， 滤液即为高温液态水水解液；
b) 步骤 a)过滤后的残渣在 160- 220 °C， 2.0- 5.0MPa，质量百分浓度为 0.01-0.1% 的马来酸溶液中水解 10〜30min， 滤液即为马来酸水解液；
c) 步骤 a)的高温液态水水解液和步骤 b)的马来酸水解液混合得到水解原料 液。
优选地， 所述高温液态水的温度为 180〜200°C , 在这个温度范围内， 生 物质中的半纤维素能以较快的速度完成水解， 但又不会过度水解；
优选地， 所述超低马来酸的质量百分浓度为 0.06-0.08%， 在这个浓度范 围内， 生物质中的纤维素能有效完成水解， 且不会过度水解。
优选地， 所述步骤 (2)的反应条件为 190〜200°C， 氢气压力 5.0MPa。 优选地， 所述步骤 (3)的反应条件为 240〜250°C， 氢气压力 4.0MPa。 本发明与现有技术相比， 具有以下有益效果：
1. 本发明利用廉价镍基催化剂，采用两段式水相催化重整工艺对水解原料液 直接进行处理制备生物汽油， 工艺简单，部分性质活泼的有机物在低温段 加氢转化，避免了在高温段聚合结焦积碳， 从而避免了催化剂容易积碳失 活等不利因素； 且产品能自动分层分离， 避免了产品精馏提纯等工艺。
2. 本发明以木质纤维素类生物质为原料制备生物汽油， 原料来源广泛而低 廉， 产品可直接利用于现有的车载发动机系统， 具有良好的市场前景， 开 辟了一条以生物质为原料制备高品位液体燃料油的新方法。
3. 本发明采用高温液态水和超低弱酸 -马来酸联合水解生物质， 使生物质水 解彻底， 而且由于马来酸酸度非常低， 减轻了对设备的腐蚀性。水解原料 液无需进行脱毒处理直接进入催化重整系统进行水相催化重整制备生物 汽油。 附图说明
图 1为本发明由水解原料液水相催化重整制备生物汽油的工作流程示意图； 附图标记： 1、 水解液储罐； 2、 计量注射泵； 3、 低温重整反应器； 4、 高温 重整反应器； 5、 冷凝器； 6、 气液分离器； 7、 吸收罐； 8、 相分离器； 9、 氢气流量计； 10、 液位控制电磁阀。 具体实施方式
下面结合实施例对本发明内容做进一步详细说明， 但对本发明不构成限制 实施例 1-3是高温液态水 -超低马来酸联合水解制备水解原料液的方法。 实施例 1 :
水解原料液的制备方法， 包括以下步骤：
(1) 20克木屑粉在 500ml 200 °C、压力 5.0MPa的高温液态水里进行水解， 水 解时间 90min; 水解完成后过滤， 滤液 (即高温液态水水解液)直接进入水解液储 槽 1，
(2)过滤后的水解残渣在浓度为 0.1Wt.%的 500ml超低马来酸溶液中继续进行 水解 30min (水解条件： 220 Ό , 5.0MPa)后过滤； 滤液即为超低马来酸水解液；
(3) 弃去未能水解的木质素， 超低马来酸水解液进入水解液储槽 1与高温液 态水水解液混合， 形成水解原料液。 实施例 2:
水解原料液的制备方法， 高温液态水温度为 200 、 压力 4.0MPa， 水解时 间 65min; 0.06\¥1.%马来酸溶液中， 190 °C， 压力 3.0MPa水解 15min， 其余操作 方式、 反应条件与实施例 1相同。 实施例 3 :
水解原料液的制备方法， 高温液态水温度为 180 °C；、 压力 2.0MPa， 水解时 间 40min; 0.01\¥1.%马来酸溶液中， 160 °C， 压力 2.0MPa水解 10min， 其余操作 方式、 反应条件与实施例 1相同。 对实施例 1-3的水解结果进行测定， 结果见表 1。 从表 1可以看出： 实施例 2的结果是比较理想的， 其水解条件相对温和， 尽管总转化率不及实施例 1， 但 其水解液中的单糖浓度是最高的， 有利于后续的水相催化重整反应。 各实施例水解结果
总转化率 单糖浓度
(wt.% ) ( g/D
实施例 1 60.6 8.19 实施例 2 53.8 9.69 实施例 3 39.7 7.11 实施例 4-6是以实施例 2所得水解原料液为原料进行水相催化重整反应。 实施例 4:
由水解原料液水相催化重整制备生物汽油的方法， 包括以下步骤：
(1) 水解原料液由计量注射泵 2 从低温重整反应器 3 底部进入填充有 Ni/Al203-Si02催化剂的低温重整反应器 3中， 由 H2气流夹带进入催化剂床层进 行反应。 反应温度为 190°C， 氢气压力为 5.0MPa。
(2) 从低温重整反应器 3出来的反应物在压差作用下直接由高温重整反应器 4底部进入填充有 Ni/HZSM-5催化剂的高温重整反应器 4， 由 H2气流夹带进入 催化剂床层进行反应。 反应温度为 240°C， 氢气压力为 4.0MPa。
(3) 从高温重整反应器 4出来后的反应物冷凝后进行气液分离， 经冷凝器 5 后直接进入气液分离器 6， 氢气和未冷凝的反应产物 (生物汽油)经气液分离器 6 上部出气出来， 减压后进入吸收罐 7; 吸收液为。6垸烃， 未吸收的气体由吸收 罐 7上部出口排出。
(4)气液分离器 6下部的液体 (水、 反应产物和未反应的糖类及多元醇等)逐 渐积累， 当液位上升到设定值后， 液位控制电磁阔 10自动打开， 液体进入相分 离器 8进行相分离； 水、 多元醇及未反应的糖组成的水相在相分离器 8下层， 反 应产物即生物汽油在相分离器 8的上层。 实施例 5:
一种由水解原料液催化重整制备生物汽油的方法，除低温催化反应器反应温 度为 160°C、压力为 4.0MPa，高温催化反应器反应温度为 210°C、压力为 2.0MPa， 其余操作方式、 反应条件与实施例 4相同。 实施例 6:
一种由水解原料液催化重整制备生物汽油的方法，除低温催化反应器反应温 度为 210°C、压力为 6.5MPa，高温催化反应器催化温度为 270V、压力为 5.6MPa， 其余操作方式、 反应条件与实施例 4相同。 对实施例 4-6中水解原料液中总碳转化率与催化反应后产物分布情况进行测 定， 结果见表 2。 表 2中的结果表明， 水解原料液在低温催化反应器中反应温度 为 190°C , 压力为 5.0MPa,高温催化反应器反应温度为 240°C , 压力为 4.0MPa时 (即实施例 4的反应条件)碳转化率最高， 产品中的 C5、 C6、 C7含量总计达 74.9% (mol 百分比）， 在这一水相重整反应工艺条件下， 水解液中的碳转化率与产品 中 C5及 C6、 07的选择性达到了较好的组合， 在这一工艺条件下生物汽油的产率 是最高的。
表 2 水解原料液水相催化重整反应结果
水解液中碳 ^ C4 C5 C6 C7 转化率 mol% mol% mol mol% mol% 实施例 4 71.7 25.1 35.2 36.6 3.1 实施例 5 61.1 17.3 31.8 48.9 2.0 实施例 6 73.9 32.7 36.1 29.5 1.7

Claims

权利 要 求
1、 一种木质纤维素类生物质水解重整制备生物汽油的方法， 其特征在于： 包括 以下步骤：
(1)水解木质纤维素类生物质得到水解原料液；
(2)水解原料液进入填充有 Ni/Al203-Si02催化剂的低温重整反应器， 160-210°C , 氢气压力 4.0〜6.5MPa条件下进行反应；
(3)从低温重整反应器出来的反应物进入填充有 Ni/HZSM-5催化剂的高温重 整反应器， 210〜270°C， 氢气压力为 2.0〜5.6MPa条件下进行反应； (4)从高温重整反应器出来后的反应物冷凝后进行气液分离， 未冷凝的生物 汽油减压后由吸收液 c6垸烃吸收； 液体经相分离器进行相分离， 在相分 离器的上层得到生物汽油。
2、 根据权利要求 1所述的木质纤维素类生物质水解重整制备生物汽油的方法， 其特征在于： 所述步骤 (1)的水解原料液是通过以下步骤得到的：
a) 木质纤维素类生物质在压力为 2.0-5.0MPa的高温液态水介质中水解 40〜
90min后过滤， 滤液即为高温液态水水解液；
b) 步骤 a)过滤后的残渣在 160-220 °C，2.0-5.0MPa，质量百分浓度为 0.01-0.1% 的马来酸溶液中水解 10〜30min， 滤液即为马来酸水解液；
c) 步骤 a)的高温液态水水解液和步骤 b)的马来酸水解液混合得到水解原料 液。
3、 根据权利要求 2所述的木质纤维素类生物质水解重整制备生物汽油的方法， 其特征在于： 所述高温液态水的温度为 180〜200°C。
4、 根据权利要求 2所述的木质纤维素类生物质水解重整制备生物汽油的方法， 其特征在于： 所述马来酸溶液的质量百分浓度为 0.06-0.08%。
5、 根据权利要求 1所述的木质纤维素类生物质水解重整制备生物汽油的方法， 其特征在于： 所述步骤 (2)的反应条件为 190〜200°C， 氢气压力 5.0MPa。
6、 根据权利要求 1所述的木质纤维素类生物质水解重整制备生物汽油的方法， 其特征在于： 所述步骤 (3)的反应条件为 240〜250°C， 氢气压力 4.0MPa。
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