WO2018058954A1 - 一种废油脂直接制备正异构烷烃的方法 - Google Patents

一种废油脂直接制备正异构烷烃的方法 Download PDF

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WO2018058954A1
WO2018058954A1 PCT/CN2017/082361 CN2017082361W WO2018058954A1 WO 2018058954 A1 WO2018058954 A1 WO 2018058954A1 CN 2017082361 W CN2017082361 W CN 2017082361W WO 2018058954 A1 WO2018058954 A1 WO 2018058954A1
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oil
catalyst
alkanes
bed reactor
waste
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PCT/CN2017/082361
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French (fr)
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王耀
王继元
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南京康鑫成生物科技有限公司
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Publication of WO2018058954A1 publication Critical patent/WO2018058954A1/zh

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    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C10G3/56—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds suspended in the oil, e.g. slurries, ebullated beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • 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 invention relates to the field of preparation of organic compounds, in particular to a method for directly preparing a normal isoparaffin from waste oil.
  • the production of clean fuels from bio-oils mainly uses hydrogenation technology.
  • the main component of vegetable oil is a linear higher fatty acid and an ester of glycerol (triglyceride), which mainly undergo hydrodeoxygenation, hydrocracking and isomerization under the action of a catalyst:
  • Chinese patent CN103289824A transformation process of fats and oils uses fats and fats as raw materials, and the raw materials are contacted with hydrogen on the catalyst, and a hydrocarbon compound is formed by one-step catalytic reaction.
  • the catalyst involved is supported.
  • M1 is an active metal component
  • [Sup] is an acidic carrier component, which can be used.
  • a hydrocarbon compound having a high cetane number, a low freezing point, and a main composition of C11 to C24 isoparaffins is produced from fats and oils.
  • the resulting C6-C12 alkane can be used as a feedstock for steam cracking to produce olefins.
  • the method realizes the purpose of preparing C6-C12 alkane by replacing the gradually reduced petroleum resources with renewable biological resources animal oil and/or vegetable oil, and broadens the raw material range of basic organic chemicals; the yield of C6-C12 alkane is high, The components are concentrated.
  • the SAPO-11 molecular sieve with mesoporous structure was prepared by impregnation method with Ni/SAPO-11 catalyst with different Ni loading.
  • the larger surface area and mesoporous structure of SAPO-11 can disperse Ni, which makes the Ni particle size smaller.
  • the weak/medium strong acid properties of Ni/SAPO-11 catalyst and its matched metal-acid dual function can significantly inhibit the carbon deposition reaction and improve the life of the catalyst.
  • the rate is as high as 70% and the isoparaffin selectivity exceeds 80%. "Progress in Chemical Industry", Vol. 26, No. 10, 2007, pp.
  • the reaction temperature is 200-500 ° C, the pressure is 2-15 MPa, the hydrogen and the reaction raw materials can be cocurrently and can be operated countercurrently;
  • the second stage is a hydroisomerization section, the catalyst used contains metal elements, molecular sieves and The carrier, the metal elements are Pd, Pt, the molecular sieves are SAPO-11, SAPO-41, ZSM-22 and ZSM-23, the carrier is Al 2 O 3 or SiO 2 , and the hydrogen and the reaction raw materials in the isomerization section are operated by countercurrent operation.
  • the reaction temperature is 200 to 500 ° C and the pressure is 2 to 15 MPa.
  • the high temperature, low pressure or low hydrogen to oil ratio can inhibit the hydrogenolysis of esters, carboxylic acids and aldehydes and the formation of alcohols, and promote the deoxidation of oils and fats selectively to the direction of decarboxylation and decarbonylation; the yield of isoparaffins increases with temperature or is empty The speed decreases first and then increases and then decreases, but the reaction pressure and hydrogen-oil ratio have little effect.
  • the above research and reports on the production of normal isoparaffins from vegetable oils are mainly carried out by a two-step process.
  • the first step of the two-step process is the hydrogenation and deoxidation of oils to produce normal paraffins, water and other by-products;
  • the step is to produce isoparaffins and short-chain paraffins by hydroisomerization or cracking for the purified para-paraffins.
  • the two-step process is multi-step integration, the oil hydrogenation, deoxidation process and alkane isomerization process are carried out on different reactors and different catalysts respectively. Therefore, the whole process requires multiple reactors, multi-step operation processes, and complicated processes. The hydrogen consumption and energy consumption are high, and the investment in production equipment is large.
  • Chinese patent CN101899318A (a method for preparing diesel hydrocarbons by catalytic hydrodeoxygenation of vegetable oils and fats) is prepared by catalytic hydrodeoxygenation of vegetable oils and fats to obtain high calorific value alkanes, which is prepared by a one-pot reaction process as follows: in the reactor Adding molybdenum carbide catalyst, vegetable oil and solvent, charging hydrogen, stirring and heating, reaction pressure is 1-10MPa, reaction temperature is 250-350 ° C, reaction is stopped after 3-10h reaction, after cooling to room temperature, filtering A diesel-based hydrocarbon containing a high calorific value alkane can be obtained by separating the catalyst.
  • Chinese patent CN101709225A (method of catalytic hydrogenation and deoxidation of vegetable oil to prepare diesel oil component) is obtained by catalytic hydrodeoxygenation of vegetable oil and fat to obtain high calorific value alkane.
  • plant oil, barium sulfate supported palladium catalyst and n-hexane are added.
  • Chinese patent CN105218289A discloses a method for preparing long-chain alkanes by in-situ hydrodecarboxylation of unsaturated fatty acids, including: 1) in a high temperature and high pressure reactor Adding unsaturated fatty acid, non-precious metal catalyst, hydrogen donor and water; 2) heating to 300-390 ° C for decarboxylation 1 ⁇ 6h; 3) decarboxylation product cooling, filtering to obtain liquid phase product and solid phase catalyst; 4) liquid The phase product is separated and layered, and the organic phase and the aqueous phase are separated, and the organic phase is analyzed by gas chromatography to obtain the yield of the long-chain alkane.
  • the solid catalyst can be reused after being washed and dried, and the non-precious metal catalyst is preferably Cu-Ni double. Active metal supported catalyst.
  • the hydrogen consumption of the reaction process is high, and since the hydrogen supply agent is added during the reaction, the production cost is further increased.
  • the present invention proposes a simple process, easy operation, and hydrogen.
  • a method for directly preparing a normal isoparaffin from waste oil comprising the following steps:
  • the mixed gas of C1-C4 alkane, CO 2 , H 2 O and unreacted H 2 produced by the reaction is treated by a demister located at the top of the slurry bed reactor and then enters the separation system, and the reaction produces C5-C22.
  • An alkane, a small amount of a C1 to C4 alkane dissolved in a C5 to C22 alkane, a mixed gas of CO 2 , H 2 O, and H 2 , and a catalyst particle slightly entrained by a C5 to C22 alkane flow out of the slurry bed reactor.
  • the filter is filtered and then enters the flashing tower.
  • the C5-C22 alkane at the bottom of the flash column is used as a backwashing oil to backflush the catalyst particles into the slurry bed reactor. Until the pressure difference disappears;
  • a small amount of mixed gas of C1 to C4 alkane, CO 2 , H 2 O, and H 2 discharged from the top of the flash column is also processed into a separation system to finally obtain a desired C5 to C22 alkane from the bottom of the flash column. It includes normal paraffins and isoparaffins.
  • the waste oil is a mixture of one or more of waste vegetable oil, waste animal fat, and food waste oil.
  • waste vegetable oil is selected from the group consisting of rapeseed oil, peanut oil, soybean oil, corn oil, rice oil, palm oil, jatropha oil, rice bran oil, castor oil, coconut oil, tall oil, olive oil.
  • rapeseed oil peanut oil, soybean oil, corn oil, rice oil, palm oil, jatropha oil, rice bran oil, castor oil, coconut oil, tall oil, olive oil.
  • waste animal fat is selected from one or more of lard, butter, sheep oil, chicken oil, and fish oil.
  • the volume fraction of CO in the H 2 containing CO in the step (1) is 5% to 50%.
  • volume fraction of CO in the H 2 containing CO in the step (1) is 10% to 30%.
  • the catalyst in the step (2) is composed of NiO, SiO 2 and Al 2 O 3 , and the mass content of NiO is 10-20%, and the mass content of SiO 2 is 40-60, based on the mass of the catalyst. %, Al 2 O 3 has a mass content of 20 to 50%.
  • the catalyst is prepared by uniformly mixing a silica sol, an aluminum sol and nickel nitrate, and spraying the mixture into a furnace of 400-600 ° C by a spray system to obtain NiO having a particle diameter of 50-100 ⁇ m.
  • the catalyst mass transfer diffusion resistance at this particle size is small, and the acidity of the catalyst is moderate, which is beneficial to convert normal paraffins into isoparaffins and avoid further cracking into low molecular weight normal structures. Alkane or isoparaffin.
  • the instantaneous mass concentration of the catalyst in the step (2) in the slurry bed reactor is from 10% to 30%.
  • reaction condition of step (2) is: temperature 250-350 ° C, pressure 2-4 MPa, and the residence time of the mixture in the slurry bed reactor reactor is 0.5-2 h.
  • the present invention provides a method for directly preparing a normal isoparaffin by using waste oil and fat, using a large amount of water generated in the hydrogenation process of waste oil, adding CO to the feed H 2 , and reacting CO with water to form CO 2 . And H 2 , providing "in situ" hydrogen for hydrogenation of the oil, greatly reducing the hydrogen consumption of the reaction process.
  • the invention adopts a slurry bed reactor and can be operated at an isothermal temperature.
  • the catalyst used is a NiO/SiO 2 -Al 2 O 3 catalyst with a particle diameter of 50-100 ⁇ m, the mass transfer diffusion resistance is small, and the acidity is moderate, which is favorable for Normal paraffins are converted to isoparaffins to avoid further cracking into low molecular weight normal paraffins or isoparaffins.
  • the waste oil of the invention can be completely converted into a normal isoparaffin, the yield of the normal isoparaffin is >80%, and the hydrogen consumption in the reaction process is not more than 1%, which greatly reduces the production cost.
  • Figure 1 is a schematic representation of the reaction of a specific embodiment of the present invention.
  • 1 is a heating furnace
  • 2 is a slurry bed reactor
  • 21 is a distributor
  • 22 is a demister
  • 3 is a filter
  • 4 is a flash tower.
  • the invention utilizes a large amount of water generated in the process of hydrogenation of oil and fat, adds CO to the feed H 2 , and reacts CO and water to form CO 2 and H 2 by using a water gas shift reaction to provide “in situ” for hydrogenation of oil and fat. Hydrogen greatly reduces the hydrogen consumption of the reaction process.
  • the water gas shift reaction which represents a process for reacting CO with water to form CO 2 and H 2 , and has a reaction equation of: CO + H 2 O ⁇ CO 2 + H 2 .
  • a method for directly preparing a normal isoparaffin from waste oil comprises the following steps:
  • reaction mixture is subjected to a reaction with a NiO/SiO 2 -Al 2 O 3 catalyst in a slurry bed reactor 2 for 2 h under a reaction condition of a temperature of 250 ° C and a pressure of 4 MPa, and the catalyst is in a slurry.
  • the instantaneous mass concentration in the bed reactor 2 is 30%, and the NiO/SiO 2 -Al 2 O 3 catalyst can be synchronously reduced by H 2 into a metal Ni/SiO 2 -Al 2 O 3 catalyst;
  • the C5-C22 alkane at the bottom of the flashing tower 4 is used as a backwashing oil to backwash the catalyst particles. Entering the slurry bed reactor 2 until the pressure difference disappears;
  • a method for directly preparing a normal isoparaffin from waste oil comprises the following steps:
  • the mixture is upwardly flowed and contacted with the NiO/SiO 2 -Al 2 O 3 catalyst in the slurry bed reactor 2 for 0.5 h, the catalyst is
  • the instantaneous mass concentration in the slurry bed reactor 2 is 10%, and the NiO/SiO 2 -Al 2 O 3 catalyst can be synchronously reduced by H 2 to a metal Ni/SiO 2 -Al 2 O 3 catalyst;
  • the C5-C22 alkane at the bottom of the flashing tower 4 is used as a backwashing oil to backwash the catalyst particles. Entering the slurry bed reactor 2 until the pressure difference disappears;
  • a method for directly preparing a normal isoparaffin from waste oil comprises the following steps:
  • the mixture is upwardly flowed and contacted with the NiO/SiO 2 -Al 2 O 3 catalyst in the slurry bed reactor 2 for 1 h, and the catalyst is in the slurry.
  • the instantaneous mass concentration in the bed reactor 2 is 15%, and the NiO/SiO 2 -Al 2 O 3 catalyst can be synchronously reduced by H 2 into a metal Ni/SiO 2 -Al 2 O 3 catalyst;
  • the C5-C22 alkane at the bottom of the flashing tower 4 is used as a backwashing oil to backwash the catalyst particles. Entering the slurry bed reactor 2 until the pressure difference disappears;
  • a method for directly preparing a normal isoparaffin from waste oil comprises the following steps:
  • the C5-C22 alkane at the bottom of the flashing tower 4 is used as a backwashing oil to backwash the catalyst particles. Entering the slurry bed reactor 2 until the pressure difference disappears;
  • a method for directly preparing a normal isoparaffin from waste oil comprises the following steps:
  • the mixture is upwardly flowed and contacted with the NiO/SiO 2 -Al 2 O 3 catalyst in the slurry bed reactor 2 for 1 h, and the catalyst is in the slurry.
  • the instantaneous mass concentration in the bed reactor 2 is 20%, and the NiO/SiO 2 -Al 2 O 3 catalyst can be synchronously reduced by H 2 to a metal Ni/SiO 2 -Al 2 O 3 catalyst;
  • the C5-C22 alkane at the bottom of the flashing tower 4 is used as a backwashing oil to backwash the catalyst particles. Entering the slurry bed reactor 2 until the pressure difference disappears;
  • a method for directly preparing a normal isoparaffin from waste oil comprises the following steps:
  • waste vegetable oil, waste animal fat and food waste oil with a mass ratio of 1:1:1 are blended into the required waste oil, and the waste oil with a volume ratio of 90:1 and H 2 containing 25% CO are used.
  • Premixing preheating through the heating furnace 1 and then entering the distributor 21 at the bottom of the slurry bed reactor 2 for secondary mixing to form a mixture;
  • the mixture is upwardly flowed and contacted with the NiO/SiO 2 -Al 2 O 3 catalyst in the slurry bed reactor 2 for 1 h, and the catalyst is in the slurry.
  • the instantaneous mass concentration in the bed reactor 2 is 20%, and the NiO/SiO 2 -Al 2 O 3 catalyst can be synchronously reduced by H 2 to a metal Ni/SiO 2 -Al 2 O 3 catalyst;
  • the C5-C22 alkane at the bottom of the flashing tower 4 is used as a backwashing oil to backwash the catalyst particles. Entering the slurry bed reactor 2 until the pressure difference disappears;
  • the raw materials are contacted with hydrogen on the catalyst by using fats and oils as a raw material, and a hydrocarbon compound is formed by a one-step catalytic reaction.
  • the catalyst used is a supported metal/supported catalyst Pt/SAPO-11, which has catalytic activity for converting a grease into a hydrocarbon compound by a one-step reaction.
  • Pt is an active metal component
  • SAPO-11 is acidic. Carrier component.
  • the product produced is a hydrocarbon compound having a high cetane number, a low freezing point, and a main composition of C11 to C24 isoparaffins, which can be used as diesel and/or aviation kerosene.
  • the conversion ratio of the oil and fat of the comparative example was 100%, and the yield of the C11 to C24 alkane was about 80%, wherein the selectivity of the isoparaffin was more than 60%, and the hydrogen consumption during the reaction was 2.5%.
  • the conversion rate of fats and oils (%) 1 - the amount of unconverted oil and fat, the amount of oil and fat raw materials ⁇ 100%
  • Hydrogen consumption (%) (amount of H 2 before reaction - amount of H 2 after reaction) Feed amount of waste oil ⁇ 100%
  • the waste oil of the method of the present invention can be completely converted into a normal isoparaffin, the yield of C5-C22 alkane is >80%, and under the optimal reaction conditions, the content of isoparaffin is >90. %, the hydrogen consumption of the reaction process is not more than 1% at most, which is much lower than the hydrogen consumption of the comparative example, which can greatly reduce the production cost and has broad application prospects.

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Abstract

一种废油脂直接制备正异构烷烃的方法，利用废油脂加氢过程中产生的大量水，在进料H2中添加CO，将CO和水进行反应生成CO2和H2，为油脂加氢提供"原位"氢，大大降低反应过程的氢耗。通过采用浆态床反应器，可以实现近乎等温操作；采用的催化剂是颗粒直径为50-100μm的NiO/SiO2-Al2O3催化剂，传质扩散阻力很小，酸性适中，有利于将正构烷烃转化为异构烷烃，通过本方法正构烷烃的收率>80%，反应过程的氢耗最高不超过1%，大大降低了生产成本。

Description

一种废油脂直接制备正异构烷烃的方法 技术领域
本发明涉及有机化合物的制备领域，尤其涉及一种废油脂直接制备正异构烷烃的方法。
背景技术
随着全球化石能源日益短缺，市场需要生产大量的清洁燃料。生物油脂作为可再生资源，得到世界的广泛重视。近年来，利用固体酸、碱催化剂催化生物油脂与甲醇或乙醇进行酯交换制备生物柴油的技术得到广泛研究，但所得的生物柴油主要为脂肪酸甲酯或乙酯，其含氧量高、热值低，无法直接用于内燃机。此外，酯交换过程中产生大量副产物甘油，增加了生产成本。因此，采用新的工艺，对生物油脂加氢脱氧、脱羧、脱羰等方式转变为直接烷烃，获得清洁的可再生汽柴油引起了广泛的关注。
当今废弃油脂重回餐桌等食品安全问题时刻困扰着人们。为了达到节约资源、保护生态环境的目的，减少乃至杜绝废弃餐饮油脂重回餐桌的现象，利用我国产量丰富的可再生的生物质资源和废弃餐饮油脂为原料制备无毒、节能环保和高性价比的烷烃具有重要的环境效益和经济效益。
目前，由生物油脂生产清洁燃料主要使用加氢技术。例如，植物油的主要成分是直链高级脂肪酸和甘油生成的酯(甘油三酯)，在催化剂的作用下主要发生加氢脱氧、加氢裂化和异构化反应：
Figure PCTCN2017082361-appb-000001
现已有一些相关研究以及报道，例如：中国专利CN103289824A(油脂的转化过程)以油脂为原料，在催化剂上使原料与氢气接触，经一步催化反应生成烃类化合物，所涉及的催化剂为担载型金属/载体催化剂M1-[Sup]，其具有使油脂经一步反应转化为烃类化合物的催化活性，催化剂的组成中，M1为活性金属组分，[Sup]为酸性载体组分，可以用于以油脂为原料生产具有高十六烷值、低凝 固点、主要组成为C11～C24异构烷烃的烃类化合物。所涉及的过程中，油脂转化为C11～C24烷烃的收率大于70％，其中，异构烷烃的选择性大于60％。中国专利CN101462915(一种C6-C12烷烃的制备方法)在加氢裂化条件下和在氢气存在下，将加氢裂化反应原料与加氢裂化催化剂接触，所述加氢裂化反应原料含有氢气以及动物油脂和/或植物油脂。该发明提供的方法能够高效制备C6－C12烷烃，而完全不同于现有技术中在加氢处理催化剂和加氢处理条件下由动物油脂和/或植物油脂制得的C15－C18烷烃。所得C6－C12烷烃可用作蒸汽裂解制烯烃的原料。该方法实现了由可再生的生物资源动物油脂和/或植物油脂替代逐步减少的石油资源制备C6－C12烷烃的目的，拓宽了基本有机化学品的原料范围；C6－C12烷烃的收率高、组分集中。《催化学报》2014年第35卷第5期第748-756页的一篇“Ni/SAPO-11催化剂上棕榈油加氢脱氧制异构烃燃料”的文献采用水热法介成了小粒、具有介孔结构的SAPO-11分子筛，采用浸渍法制备了不同Ni负载量的Ni/SAPO-11催化剂，SAPO-11较大表面积和介孔结构可分散Ni，使得Ni粒子尺寸较小。在棕榈油加氢脱氧制备液体烃类燃料反应中，Ni/SAPO-11催化剂的弱/中强酸性质及其匹配的金属-酸双功能可显著抑制积炭反应，提高催化剂的寿命，液体烷烃收率高达70％，异构烷烃选择性超过80％。《化工进展》2007年第26卷第10期第1391-1394页的一篇“植物油加氢制备高十六烷值柴油组分研究进展”的文献介绍了植物油加氢制备柴油的主要化学反应、工艺方法以及该项技术的工业化状况，分析了植物油直接加氢、先加氢后异构、直接脱羧工艺以及植物油与矿物柴油掺炼工艺的特点。其中植物油加氢脱氧得到直链烷烃再临氢异构制备高十六烷值柴油组分的新工艺包括两段，第一段为加氢脱氧段，采用氧化铝或氧化硅负载的Co-Mo或Ni-Mo类催化剂，反应温度200～500℃，压力2～15MPa，氢气与反应原料可并流也可逆流操作；第二段为加氢异构段，所用催化剂包含有金属元素、分子筛和载体，金属元素为Pd、Pt，分子筛为SAPO-11、SAPO-41、ZSM-22及ZSM-23，载体为Al2O3或SiO2，异构段中氢气和反应原料采用逆流操作方式，反应温度200～500℃，压力2～15MPa。《催化学报》2013年第34卷第6期第1128-1138页的一篇“反应条件对Pt/SAPO-11催化油脂一步加氢制异构烷烃的影响”的文献以大豆油为模型原料，研究了反应温度、压力、氢油比和空速等条件对Pt/SAPO-11催化油脂一步加氢制异构烷烃反应的影响，并分析了反应中间产物、气体产物(CO,CO2)及烷烃终产物的变化趋势。认为高温、低压或低氢油比可抑制酯、羧酸和醛的氢解以及醇的生成，促进油脂脱氧选择性地向脱羧和脱羰方向进行；异构烷烃收率随温度升高或空速减小而先增加后下降，但反应压力和氢油比的影响不大。
上述研究和报道中由植物油生产正异构烷烃的过程主要依靠两步法实现，两步法工艺的第一步为油脂经加氢、脱氧生产正构烷烃、水和其他一些副产物；第二步为经过分离净化后的正构烷烃通过加氢异构化反应或裂化反应生产异构烷烃和短支链烷烃。由于两步法过程为多步集成，油脂加氢、脱氧过程和烷烃异构化过程分别在不同反应器和不同催化剂上进行，因此，整个过程需要多个反应器、多步操作工序，工艺复杂，氢耗和能耗高，对生产设备的投资大。
此外，除了固定床两步法工艺之外，还有在高压反应釜中一步法反应工艺的报道。例如，中国专利CN101899318A(一种植物油脂催化加氢脱氧制备柴油类烃的方法)采用植物油脂经催化加氢脱氧制得高热值烷烃，采用一锅法反应工艺制备，方法如下：在反应器中，加入碳化钼催化剂，植物油脂和溶剂，充入氢气，开启搅拌和加热，反应压力为1-10MPa，反应温度为250-350℃，反应3-10h后停止反应，待冷却至室温后，过滤分离出催化剂即可得到含高热值烷烃的柴油类烃。中国专利CN101709225A(植物油脂催化加氢脱氧制备柴油组分的方法)以植物油脂经催化加氢脱氧制得高热值烷烃，在反应器中，加入植物油脂，硫酸钡负载钯催化剂和正己烷、正庚烷、正辛烷或十二烷中的一种溶剂，充入氢气，反应压力1-10MPa，开启搅拌和加热，温度为230-320℃，反应3-12h后停止反应，待冷却至室温后，催化剂和液相产物自动分离，无需离心、过滤等繁杂的后处理即可得到含高热值烷烃的柴油组分。中国专利CN105218289A(一种不饱和脂肪酸原位加氢脱羧制备长链烷烃的方法)公开了一种不饱和脂肪酸原位加氢脱羧制备长链烷烃的方法，包括：1)在高温高压反应釜中加入不饱和脂肪酸、非贵金属催化剂、供氢剂和水；2)加热升温至300～390℃脱羧反应1～6h；3)脱羧产物冷却，过滤后得到液相产物和固相催化剂；4)液相产物静置分层后分液得到有机相和水相，有机相用气相色谱分析得到长链烷烃的收率，固体催化剂经清洗干燥后即可重复使用，非贵金属催化剂优选为Cu-Ni双活性金属负载型催化剂。但是该反应工艺的氢耗较高，并且由于在反应过程中加入供氢剂，反而进一步增加了生产成本。
针对上述利用油脂生产烷烃的技术均存在一定的缺陷以及生产成本较高的问题，需要一种新的技术方案来解决上述问题。
发明内容
发明目的：为了克服现有技术中存在的多步骤操作工艺复杂、氢耗能耗较高、生产设备成本投资大、成本较高的缺陷，本发明提出了一种工艺设备简单、易操作、氢耗能耗低、投资小、收率高的废油脂直接制备正异构烷烃的方法。
技术方案：为了解决上述技术问题，本发明所采用的技术方案为：
一种废油脂直接制备正异构烷烃的方法，包括以下步骤：
(1)将体积比为50:1-100:1的废油脂与含有CO的H2进行预混合，经过加热炉预热后进入位于浆态床反应器底部的分配器进行二次混合均匀形成混合物料；采用浆态床反应器，可以进行几乎等温操作，这对于加氢脱氧强放热反应更加有利；
(2)混合物料向上流动与浆态床反应器中的催化剂进行接触进行反应；
(3)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器顶部的除沫器处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器，经过滤器过滤后进入闪蒸塔，当过滤器被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器中，直至压差消失；
(4)从闪蒸塔顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
更为优选的，所述废油脂为废植物油脂、废动物油脂、餐饮废油中的一种或多种混合。
更进一步的，所述废植物油脂选自菜籽油、花生油、大豆油、玉米油、稻米油、棕榈油、麻风树油、米糠油、蓖麻油、椰子油、妥尔油、橄榄油中的一种或者多种混合。
更进一步的，所述废动物油脂选自猪油、牛油、羊油、鸡油、鱼油中的一种或者多种混合。
更为优选的，步骤(1)中所述含有CO的H2中CO的体积分数为5％-50％。
更进一步的，步骤(1)中所述含有CO的H2中CO的体积分数为10％-30％。
更为优选的，步骤(2)中所述催化剂由NiO、SiO2、Al2O3组成，以催化剂的质量计，NiO的质量含量为10～20％，SiO2的质量含量为40～60％，Al2O3的质量含量为20～50％。
更进一步的，所述催化剂的制备方法为将硅溶胶、铝溶胶和硝酸镍混合均匀，采用喷雾系统将所述混合物料喷向400～600℃的炉膛中，得颗粒直径为50～100μm的NiO/SiO2-Al2O3催化剂，此粒径下的催化剂传质扩散阻力很小，且催化剂的酸性适中，有利于将正构烷烃转化为异构烷烃，避免进一步裂化成低分子量的正构烷烃或异构烷烃。
更为优选的，步骤(2)中所述催化剂在浆态床反应器中的瞬时质量浓度为10％-30％。
更为优选的，步骤(2)反应条件为：温度250-350℃，压力2-4MPa,混合物料在浆态床反应器反应器中停留时间为0.5-2h。
有益效果：本发明提供的一种废油脂直接制备正异构烷烃的方法，利用废油脂加氢过程中产生的大量水，在进料H2中添加CO，将CO和水进行反应生成CO2和H2，为油脂加氢提供“原位”氢，大大降低反应过程的氢耗。本发明采用浆态床反应器，可以进乎等温操作，采用的催化剂是颗粒直径为50～100μm的NiO/SiO2-Al2O3催化剂，传质扩散阻力很小，酸性适中，有利于将正构烷烃转化为异构烷烃，避免进一步裂化成低分子量的正构烷烃或异构烷烃。且本发明的废油脂可完全转化为正异构烷烃，正异构烷烃的收率＞80％，反应过程的氢耗最高不超过1％，大大降低了生产成本。
附图说明
图1为本发明具体实施方式的反应示意图。
其中：1为加热炉，2为浆态床反应器，21为分配器，22为除沫器，3为过滤器，4为闪蒸塔。
具体实施方式
下面结合实施例对本发明作进一步的详细说明：
本发明利用油脂加氢过程中产生的大量水，在进料H2中添加CO，利用水气变换反应，将CO和水进行反应生成CO2和H2，为油脂加氢提供“原位”氢，大大降低反应过程的氢耗。所述的水气变换反应，其表示用于CO和水反应生成CO2和H2的过程，其反应方程式为：CO+H2O→CO2+H2。
实施例1：
请参照图1，一种废油脂直接制备正异构烷烃的方法，包括以下步骤：
(1)催化剂的制备：将硅溶胶、铝溶胶和硝酸镍混合均匀，采用喷雾系统将所述混合物料喷向400℃的炉膛中，得颗粒直径为50μm的NiO/SiO2-Al2O3催化剂，以催化剂的质量计，NiO的质量含量为10％，SiO2的质量含量为40％，Al2O3的质量含量为50％，制备过程中，硅溶胶、铝溶胶和硝酸镍的添加量可根据最终催化剂的构成推算得到。
(2)将体积比为100:1的废植物油脂与含有5％CO的H2进行预混合，经过加热炉1预热后进入位于浆态床反应器2底部的分配器21进行二次混合均匀形成混合物料；
(3)在温度为250℃，压力4MPa的反应条件下,混合物料向上流动与浆态 床反应器2中的NiO/SiO2-Al2O3催化剂进行接触进行反应2h，所述催化剂在浆态床反应器2内的瞬时质量浓度为30％，所述NiO/SiO2-Al2O3催化剂可被H2同步还原为金属Ni/SiO2-Al2O3催化剂；
(4)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器2顶部的除沫器22处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器2，经过滤器3过滤后进入闪蒸塔4，当过滤器3被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔4底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器2中，直至压差消失；
(5)从闪蒸塔4顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔4底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
(6)分析结果：废植物油脂的转化率、C5～C22烷烃的收率、正异构烷烃的含量、以及反应过程的氢耗见表1。
实施例2：
请参照图1，一种废油脂直接制备正异构烷烃的方法，包括以下步骤：
(1)催化剂的制备：将硅溶胶、铝溶胶和硝酸镍混合均匀，采用喷雾系统将所述混合物料喷向600℃的炉膛中，得颗粒直径为100μm的NiO/SiO2-Al2O3催化剂，以催化剂的质量计，NiO的质量含量为20％，SiO2的质量含量为60％，Al2O3的质量含量为20％，制备过程中，硅溶胶、铝溶胶和硝酸镍的添加量可根据最终催化剂的构成推算得到。
(2)将体积比为50:1的餐饮废油与含有50％CO的H2进行预混合，经过加热炉1预热后进入位于浆态床反应器2底部的分配器21进行二次混合均匀形成混合物料；
(3)在温度为350℃，压力2MPa的反应条件下,混合物料向上流动与浆态床反应器2中的NiO/SiO2-Al2O3催化剂进行接触进行反应0.5h，所述催化剂在浆态床反应器2内的瞬时质量浓度为10％，所述NiO/SiO2-Al2O3催化剂可被H2同步还原为金属Ni/SiO2-Al2O3催化剂；
(4)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器2顶部的除沫器22处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器2，经过滤器 3过滤后进入闪蒸塔4，当过滤器3被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔4底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器2中，直至压差消失；
(5)从闪蒸塔4顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔4底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
(6)分析结果：餐饮废油的转化率、C5～C22烷烃的收率、正异构烷烃的含量、以及反应过程的氢耗见表1。
实施例3：
请参照图1，一种废油脂直接制备正异构烷烃的方法，包括以下步骤：
(1)催化剂的制备：将硅溶胶、铝溶胶和硝酸镍混合均匀，采用喷雾系统将所述混合物料喷向500℃的炉膛中，得颗粒直径为70μm的NiO/SiO2-Al2O3催化剂，以催化剂的质量计，NiO的质量含量为15％，SiO2的质量含量为50％，Al2O3的质量含量为35％，制备过程中，硅溶胶、铝溶胶和硝酸镍的添加量可根据最终催化剂的构成推算得到。
(2)将体积比为70:1的餐饮废油与含有10％CO的H2进行预混合，经过加热炉1预热后进入位于浆态床反应器2底部的分配器21进行二次混合均匀形成混合物料；
(3)在温度为300℃，压力3MPa的反应条件下,混合物料向上流动与浆态床反应器2中的NiO/SiO2-Al2O3催化剂进行接触进行反应1h，所述催化剂在浆态床反应器2内的瞬时质量浓度为15％，所述NiO/SiO2-Al2O3催化剂可被H2同步还原为金属Ni/SiO2-Al2O3催化剂；
(4)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器2顶部的除沫器22处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器2，经过滤器3过滤后进入闪蒸塔4，当过滤器3被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔4底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器2中，直至压差消失；
(5)从闪蒸塔4顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔4底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
(6)分析结果：餐饮废油的转化率、C5～C22烷烃的收率、正异构烷烃的 含量、以及反应过程的氢耗见表1。
实施例4：
请参照图1，一种废油脂直接制备正异构烷烃的方法，包括以下步骤：
(1)催化剂的制备：同实施例3；
(2)将体积比为60:1的餐饮废油与含有30％CO的H2进行预混合，经过加热炉1预热后进入位于浆态床反应器2底部的分配器21进行二次混合均匀形成混合物料；
(3)在温度为280℃，压力3MPa的反应条件下,混合物料向上流动与浆态床反应器2中的NiO/SiO2-Al2O3催化剂进行接触进行反应1.5h，所述催化剂在浆态床反应器2内的瞬时质量浓度为25％，所述NiO/SiO2-Al2O3催化剂可被H2同步还原为金属Ni/SiO2-Al2O3催化剂；
(4)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器2顶部的除沫器22处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器2，经过滤器3过滤后进入闪蒸塔4，当过滤器3被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔4底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器2中，直至压差消失；
(5)从闪蒸塔4顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔4底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
(6)分析结果：餐饮废油的转化率、C5～C22烷烃的收率、正异构烷烃的含量、以及反应过程的氢耗见表1。
实施例5：
请参照图1，一种废油脂直接制备正异构烷烃的方法，包括以下步骤：
(1)催化剂的制备：同实施例3。
(2)将体积比为80:1的餐饮废油与含有20％CO的H2进行预混合，经过加热炉1预热后进入位于浆态床反应器2底部的分配器21进行二次混合均匀形成混合物料；
(3)在温度为320℃，压力3MPa的反应条件下,混合物料向上流动与浆态床反应器2中的NiO/SiO2-Al2O3催化剂进行接触进行反应1h，所述催化剂在浆态床反应器2内的瞬时质量浓度为20％，所述NiO/SiO2-Al2O3催化剂可被H2同步还原为金属Ni/SiO2-Al2O3催化剂；
(4)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器2顶部的除沫器22处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器2，经过滤器3过滤后进入闪蒸塔4，当过滤器3被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔4底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器2中，直至压差消失；
(5)从闪蒸塔4顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔4底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
(6)分析结果：餐饮废油的转化率、C5～C22烷烃的收率、正异构烷烃的含量、以及反应过程的氢耗见表1。
实施例6：
请参照图1，一种废油脂直接制备正异构烷烃的方法，包括以下步骤：
(1)催化剂的制备：同实施例3。
(2)将质量比为1：1：1的废植物油脂、废动物油脂和餐饮废油调和成所需废油脂，将体积比为90:1的废油脂与含有25％CO的H2进行预混合，经过加热炉1预热后进入位于浆态床反应器2底部的分配器21进行二次混合均匀形成混合物料；
(3)在温度为300℃，压力3MPa的反应条件下,混合物料向上流动与浆态床反应器2中的NiO/SiO2-Al2O3催化剂进行接触进行反应1h，所述催化剂在浆态床反应器2内的瞬时质量浓度为20％，所述NiO/SiO2-Al2O3催化剂可被H2同步还原为金属Ni/SiO2-Al2O3催化剂；
(4)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器2顶部的除沫器22处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器2，经过滤器3过滤后进入闪蒸塔4，当过滤器3被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔4底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器2中，直至压差消失；
(5)从闪蒸塔4顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔4底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
(6)分析结果：废油脂的转化率、C5～C22烷烃的收率、正异构烷烃的含量、以及反应过程的氢耗见表1。
对比例1：
按照中国专利CN103289824A(油脂的转化过程)所描述的方法，以油脂为原料，在催化剂上使原料与氢气接触，经一步催化反应生成烃类化合物。采用的催化剂为担载型金属/载体催化剂Pt/SAPO-11，其具有使油脂经一步反应转化为烃类化合物的催化活性，催化剂的组成中，Pt为活性金属组分，SAPO-11为酸性载体组分。生产的产品是具有高十六烷值、低凝固点、主要组成为C11～C24异构烷烃的烃类化合物，该烃类化合物可作为柴油和/或航空煤油使用。比较例的油脂的转化率为100％，C11～C24烷烃的收率80％左右，其中，异构烷烃的选择性大于60％，反应过程的氢耗2.5％。
实施例1-6以及对比例1的分析结果见表1：
表1：实施例与对比例转化率、收率以及氢耗对比
Figure PCTCN2017082361-appb-000002
其中，油脂的转化率(％)＝1－未转化的油脂的量÷油脂原料的量×100％
C5～C22正异构烷烃的收率(％)＝C5～C22正异构烷烃的量÷已转化的油脂的量×100％
氢耗(％)＝(反应前的H2量－反应后的H2量)÷废油脂的进料量×100％
由表1的对比数据来看，本发明方法的废油脂可以完全转化为正异构烷烃，C5～C22烷烃的收率＞80％，在较优的反应条件下，异构烷烃的含量＞90％，反应过程的氢耗最大不超过1％，远低于比较例的氢耗，可大大降低生产成本，具有广阔的应用前景。
应当指出，以上具体实施方式仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落 于本申请所附权利要求所限定的范围。

Claims (10)

  1. 一种废油脂直接制备正异构烷烃的方法，其特征在于包括以下步骤：
    (1)将体积比为50:1-100:1的废油脂与含有CO的H2进行预混合，经过加热炉(1)预热后进入位于浆态床反应器(2)底部的分配器(21)进行二次混合均匀形成混合物料；
    (2)混合物料向上流动与浆态床反应器(2)中的催化剂进行接触进行反应；
    (3)反应生成的C1～C4烷烃、CO2、H2O以及未反应的H2的混合气体通过位于浆态床反应器(2)顶部的除沫器(22)处理后进入分离系统，反应生成的C5～C22烷烃、溶解在C5～C22烷烃中的少量的C1～C4烷烃、CO2、H2O、H2的混合气体、以及被C5～C22烷烃少量夹带的催化剂颗粒共同流出浆态床反应器(2)，经过滤器(3)过滤后进入闪蒸塔(4)，当过滤器(3)被夹带的催化剂颗粒堵塞产生压差时，以闪蒸塔(4)底部的C5～C22的烷烃作为反冲洗油，将催化剂颗粒反冲洗进入浆态床反应器(2)中，直至压差消失；
    (4)从闪蒸塔(4)顶部排出的少量的C1～C4烷烃、CO2、H2O、H2的混合气体也进入分离系统进行处理，最终从闪蒸塔(4)底得到所需C5～C22烷烃，包括正构烷烃和异构烷烃。
  2. 根据权利要求1所述的废油脂直接制备正异构烷烃的方法，其特征在于：所述废油脂为废植物油脂、废动物油脂、餐饮废油中的一种或多种混合。
  3. 根据权利要求2所述的废油脂直接制备正异构烷烃的方法，其特征在于：所述废植物油脂选自菜籽油、花生油、大豆油、玉米油、稻米油、棕榈油、麻风树油、米糠油、蓖麻油、椰子油、妥尔油、橄榄油中的一种或者多种混合。
  4. 根据权利要求2所述的废油脂直接制备正异构烷烃的方法，其特征在于：所述废动物油脂选自猪油、牛油、羊油、鸡油、鱼油中的一种或者多种混合。
  5. 根据权利要求1所述的废油脂直接制备正异构烷烃的方法，其特征在于：步骤(1)中所述含有CO的H2中CO的体积分数为5％-50％。
  6. 根据权利要求5所述的废油脂直接制备正异构烷烃的方法，其特征在于：步骤(1)中所述含有CO的H2中CO的体积分数为10％-30％。
  7. 根据权利要求1所述的废油脂直接制备正异构烷烃的方法，其特征在于：步骤(2)中所述催化剂由NiO、SiO2、Al2O3组成，以催化剂的质量计，NiO的质量含量为10～20％，SiO2的质量含量为40～60％，Al2O3的质量含量为20～50％。
  8. 根据权利要求7所述的废油脂直接制备正异构烷烃的方法，其特征在于：所述催化剂的制备方法为将硅溶胶、铝溶胶和硝酸镍混合均匀，采用喷雾系统将所述混合物料喷向400～600℃的炉膛中，得颗粒直径为50～100μm的NiO/SiO2-Al2O3催化剂。
  9. 根据权利要求1所述的废油脂直接制备正异构烷烃的方法，其特征在于：步骤(2)中所述催化剂在浆态床反应器中的瞬时质量浓度为10％-30％。
  10. 根据权利要求1所述的废油脂直接制备正异构烷烃的方法，其特征在于：步骤(2)反应条件为：温度250-350℃，压力2-4MPa,混合物料在浆态床反应器反应器中停留时间为0.5-2h。
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