WO2018227842A1 - Catalyst used for producing aromatic-rich biofuel, and method for preparing same - Google Patents

Catalyst used for producing aromatic-rich biofuel, and method for preparing same Download PDF

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WO2018227842A1
WO2018227842A1 PCT/CN2017/107943 CN2017107943W WO2018227842A1 WO 2018227842 A1 WO2018227842 A1 WO 2018227842A1 CN 2017107943 W CN2017107943 W CN 2017107943W WO 2018227842 A1 WO2018227842 A1 WO 2018227842A1
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biochar
catalyst
lignin
rich
solution
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卜权
摩根•赫文•马里恩
梁江辉
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江苏大学
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    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B01J35/50—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • 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
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • 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 belongs to the technical field of biomass catalytic pyrolysis, and in particular relates to a catalyst for producing an aromatic-rich biofuel and a preparation method thereof.
  • biomass energy resources including crops such as corn, wheat and rice, and residues of rice husk and sugar cane agricultural products, which can reach several hundred million tons per year.
  • Biomass has been identified as the most promising raw material for the production of renewable energy.
  • the yield and quality of the obtained liquid oil are low, the selectivity is poor, the catalyst activity is low, and it is easy to be deactivated. Therefore, it is necessary to increase the biomass pyrolysis liquid. The yield and quality of the product.
  • Biochar is a solid product formed by high-temperature pyrolysis of biomass under anaerobic anoxic state, which itself contains some mineral elements. Alkali metal elements such as Ca, Mg, Zn, etc., in addition, biochar has developed voids and specific surface area. Therefore, this study is based on biochar products formed by microwave pyrolysis biomass and is subjected to transition metal oxides. Modification, preparation of a biochar catalyst, using this biochar catalyst to solve the problem of bio-oil yield and quality in pyrolysis experiments.
  • Biomass consists mainly of cellulose, hemicellulose and lignin.
  • lignin accounts for 25% and is the second most abundant organic matter in the world (cellulose is the first).
  • Lignin is a complex phenolic polymer formed from three alcohol monomers (coumaryl alcohol, coniferyl alcohol, sinapyl alcohol).
  • coumaryl alcohol, coniferyl alcohol, sinapyl alcohol a complex phenolic polymer formed from three alcohol monomers.
  • coumaryl alcohol, coniferyl alcohol, sinapyl alcohol coumaryl alcohol, coniferyl alcohol, sinapyl alcohol
  • this study intends to prepare lignin-derived biochar by microwave-assisted pyrolysis and load transition metal oxygen on the surface of biochar produced to regulate the physicochemical properties of lignin-derived biochar catalyst.
  • the conversion rate of raw materials is increased, the formation of carbon deposits is reduced, and the activity, selectivity and service life of the catalyst are improved.
  • the object of the present invention is to provide a catalyst for producing an aromatic hydrocarbon-rich biofuel and a preparation method thereof, so as to obtain a modified catalyst, thereby improving liquid yield and quality in biomass catalytic pyrolysis reaction, specifically in improving raw materials.
  • the conversion rate and the chemical component selectivity of the bio-oil reduce the formation of catalyst coke and increase the activity and selectivity of the catalyst.
  • the present invention uses lignin microwave pyrolysis to derive biochar as a catalyst carrier raw material, reveals the influence of the supported transition metal oxide on the prepared biochar catalyst, and analyzes the prepared transition metal by XRD, SEM and other analytical means.
  • the microscopic morphology of the modified biochar catalyst, the combination of the active component and the carrier, and the distribution state are as follows:
  • a method for preparing a catalyst for producing an aromatic-rich biofuel characterized by comprising the steps of:
  • Step one microwave pyrolysis of lignin to obtain biochar;
  • the lignin raw material is weighed according to the required amount and placed in a quartz flask reactor, and the microwave pyrolysis parameter is set to a reaction temperature of 500 ° C, and the microwave power is 750 W,
  • the lignin pyrolysis reaction occurs more completely, so that pure biochar is obtained, and the reaction time is set to 30 minutes;
  • Step 2 Preparation of biochar powder: The biochar is poured out from the quartz flask reactor and cooled to room temperature; since the lignin is pyrolyzed in the microwave, it is easy to form a block-like biochar product.
  • the lignin-derived biochar produced by microwave pyrolysis is first pulverized into fine powder, and then sieved to ensure uniformity of size, thereby obtaining a biochar powder;
  • Step three repeatedly washing the biochar powder with deionized water to remove contaminants from the biochar powder structure and open the surface pores of the biochar to obtain pure biochar powder;
  • Step 4 drying the pure biochar powder in an oven at 105 ° C for 15 h to remove excess water to obtain a dried biochar powder;
  • Step 5 dissolving the weighed zinc salt in deionized water to obtain a solution A, and adding the dried biochar powder to the solution A under continuous stirring to obtain a solution B; the metal element in the zinc salt The mass ratio is 5% of the selected biochar;
  • Step six using a magnetic stirrer to continuously stir the solution B, to obtain a solution C;
  • Step 7 the solution C is subjected to suction filtration and molding to obtain a shaped columnar particulate material, which is then dried in an oven to obtain a product 1;
  • Step 8 calcining the product one through a high-temperature tube furnace in a mixed gas atmosphere of nitrogen and hydrogen to crystallize and shape, thereby preparing a final product, that is, a modified biochar catalyst loaded with a transition metal;
  • the volume ratio of nitrogen to hydrogen in the mixture is 99:1.
  • the lignin raw material in the first step is a commercial lignin.
  • the zinc salt in the fifth step is Zn(NO 3 ) 2 .6H 2 O, and the mass ratio of the zinc salt to the dried biochar powder is 5%.
  • Step 6 specifically, the solution B was placed on a magnetic stirrer, a magnetic stir bar was added to the solution, and stirring was continued for 6 hours in a water bath at 60 ° C.
  • the step 7 is specifically: suction filtration, molding is to put a layer of filter paper in the Buchner funnel and then connect the Buchner funnel to the vacuum pump, and the solution C is suction filtered in the prepared Buchner funnel, and the filter paper is retained after the suction filtration.
  • the residue was then made into a columnar particle having a diameter of 5 mm and a length of 7 mm using a plastic tube to facilitate use in experiments.
  • Step 7 The drying conditions were specifically vacuum dried in an electric oven at 105 ° C for 15 h.
  • step 8 in a tube furnace, a mixed gas having a flow rate of 60 mL/min was used to maintain an oxygen-deficient atmosphere, and crystallization was performed at a temperature of 550 ° C for 4 hours.
  • a catalyst for producing an aromatic-rich biofuel which is produced by the above method.
  • the present invention has a beneficial effect.
  • the transition metal modified biochar catalyst prepared in the invention maintains the characteristic mode of the biochar topology, and the modified biochar catalyst still maintains a regular structure. It shows that the dispersibility of the modified biochar catalyst is still good.
  • the XRD pattern of the biochar modified with zinc salt has a more prominent peak than the unmodified biochar catalyst, which is a high crystal formed by substances other than the framework material, and also indicates the peak. It is caused by the addition of zinc, while the other peaks are consistent with the peak of the biochar catalyst. From the SEM analysis, the main crystal particles and their agglomerates can be slightly changed in the sample with the addition of zinc salt. Compared with the biochar without metal addition, the single crystal size of the zinc-doped sample is slightly reduced, and the surface is slightly reduced. More smooth.
  • Figure 1 is an XRD diffraction pattern of the effect of the zinc salt of the present invention on a modified biochar catalyst
  • FIG. 3 is an analysis diagram of the bio-oil component of the modified catalyst and the un-catalyzed lignin/PE microwave co-pyrolysis reaction product of the present invention
  • FIG. 4 is a flow chart of a method of the present invention.
  • FIG. 40 g of the lignin biomass feedstock was weighed and placed in the reaction flask without the addition of a heating agent, so that the resulting coke was as pure as possible. Nitrogen gas was introduced for 15 min before the start of the experiment to maintain an oxygen-free atmosphere.
  • the microwave pyrolysis parameter was set to a reaction temperature of 500 ° C and a microwave power of 750 W. In order to make the lignin pyrolysis reaction more complete, a relatively pure biochar was obtained, and the reaction time was set to 30 minutes. Since lignin is pyrolyzed in the microwave, it is easy to form a block-like biochar product.
  • the lignin-derived biochar produced by microwave pyrolysis is first pulverized into fine powder and then sieved to ensure uniformity of size. Then, the biochar powder was repeatedly washed with deionized water. After washing, it was dried in an oven at 105 ° C for 15 h to remove excess water. This gave a biochar raw material for the preparation of the catalyst.
  • the weighed 10.13 g of Zn(NO 3 ) 2 .6H 2 O was dissolved in excess deionized water, and 40 g of a biochar raw material was added thereto with constant stirring. The solution was placed on a magnetic stirrer and continuously stirred in a water bath at 60 ° C for 6 h.
  • the mixture was filtered, molded, and the formed material was vacuum dried in an electric oven at 105 ° C for 15 h. Then, an oxygen-deficient atmosphere was maintained at a flow rate of 60 mL/min in a nitrogen-hydrogen mixed atmosphere (99:1), and crystallization was carried out at a temperature of 550 ° C for 4 hours to prepare a metal-supported biochar catalyst.
  • XRD characterization was performed to compare the crystal characteristics of the metal zinc modified catalyst and the untreated catalyst, as shown in FIG.
  • the modified molecular sieve catalyst maintains the characteristic pattern of the topological structure of the procatalyst, but a prominent peak formed by the addition of metallic zinc appears, indicating that the modified metallic zinc is loaded into the biochar catalyst.
  • a catalytic pyrolysis experiment was carried out by using a catalytic fixed bed reactor in combination with a microwave pyrolysis apparatus.
  • the raw material used in the test was lignin: firstly weighed 20 g of lignin and 5 g of PE as raw materials in a quartz flask reactor with a capacity of 500 ml, and then added 1 g of activated carbon as a microwave absorbing material and lignin/polyethylene (PE). The mixture was mixed, and the quartz flask reactor was placed in a microwave oven, and 1 g of the prepared catalyst was placed in a catalytic fixed bed reactor.
  • the reaction temperature for setting microwave pyrolysis is 500 ° C, the time is 8 min, and the microwave power is 750 W.
  • the pyrolysis gas is subjected to catalytic reforming reaction through a catalytic fixed bed after microwave pyrolysis reaction, and then rapidly condensed.
  • the bio-oil was collected, and the organic components and catalysts of the bio-oil after the reaction were collected and analyzed by means of GC/MS, SEM and XRD.
  • the microwave pyrolysis experiments of the uncharged catalyst and the added metal zinc modified biochar catalyst were compared. It was found that the catalyst used was significantly more than the bio-oil obtained without the catalyst.
  • the effect of the catalyst on the bio-oil yield was: zinc-bio Carbon catalyst > no catalyst.

Abstract

Provided are a catalyst used for producing aromatic-rich biofuel, and a method for preparing same, comprising: forming lignin biochar raw material by microwave pyrolysis. Weighed zinc salt is dissolved in excess deionized water, and crushed, washed, and dried biochar powder is added while stirring; the solution is continuously stirred using a magnetic stirrer in a 60°C water bath for 6 h; then the solution is filtered and formed, and is dried for 15 h in an oven at 105°C; next, crystallization and forming are performed in an atmosphere of mixed gas, nitrogen and hydrogen (99:1), in a tube furnace at 550°C, and a modified zinc‑biochar catalyst is thus prepared. The modified catalyst increases the bio-oil yield and selectivity of aromatics obtained by lignin catalytic pyrolysis, and can be applied to the related technology of catalytic pyrolysis conversion.

Description

一种用于生产富芳烃生物燃油的催化剂及其制备方法Catalyst for producing aromatic-rich biofuel and preparation method thereof 技术领域Technical field
本发明属于生物质催化热解技术领域，具体涉及一种用于生产富芳烃生物燃油的催化剂及其制备的方法。The invention belongs to the technical field of biomass catalytic pyrolysis, and in particular relates to a catalyst for producing an aromatic-rich biofuel and a preparation method thereof.
背景技术Background technique
现今化石燃油已渐渐不能满足人类的需要，急需发现可替代的新型能源，来缓解日益紧张的能源危机问题和环境污染问题。我国作为农业大国生物质能资源广泛，包括玉米、小麦、水稻等农作物秸秆及稻谷壳、甘蔗农产品加工剩余物，每年可达几亿吨。生物质已被确定为用于生产可再生能源最有前途的原料。但是在生物质转化为液体燃油过程中仍然存在很多问题，如：所得液体油产率和品质较低，选择性较差，催化剂活性较低、易失活等，因此必须提高生物质热解液体产物的产率和品质。另外，热解过程中除了获得生物油，还会产生大量的生物炭，生物炭是由于生物质在无氧获缺氧状态下，经高温热解后形成的固体产物，其本身含有一些矿物元素如Ca,Mg,Zn等碱金属元素，此外，生物炭具有发达的空隙和比表面积，因此，本研究拟以微波热解生物质形成的生物炭产物为基础，经过过渡金属氧化物对其进行改性，制备一种生物炭催化剂，以这种生物炭催化剂来解决热解实验中生物油产率和品质等问题。Nowadays, fossil fuels have gradually failed to meet the needs of human beings, and it is urgent to find alternative new energy sources to alleviate the increasingly tense energy crisis and environmental pollution problems. As a large agricultural country, China has a wide range of biomass energy resources, including crops such as corn, wheat and rice, and residues of rice husk and sugar cane agricultural products, which can reach several hundred million tons per year. Biomass has been identified as the most promising raw material for the production of renewable energy. However, there are still many problems in the process of converting biomass into liquid fuel. For example, the yield and quality of the obtained liquid oil are low, the selectivity is poor, the catalyst activity is low, and it is easy to be deactivated. Therefore, it is necessary to increase the biomass pyrolysis liquid. The yield and quality of the product. In addition, in addition to obtaining bio-oil, a large amount of biochar is produced in the pyrolysis process. Biochar is a solid product formed by high-temperature pyrolysis of biomass under anaerobic anoxic state, which itself contains some mineral elements. Alkali metal elements such as Ca, Mg, Zn, etc., in addition, biochar has developed voids and specific surface area. Therefore, this study is based on biochar products formed by microwave pyrolysis biomass and is subjected to transition metal oxides. Modification, preparation of a biochar catalyst, using this biochar catalyst to solve the problem of bio-oil yield and quality in pyrolysis experiments.
生物质主要有纤维素、半纤维素和木质素组成。在木本植物中，木质素占25％，是世界上第二位最丰富的有机物(纤维素是第一位)。木质素是由三种醇单体(对香豆醇、松柏醇、芥子醇)形成的一种复杂酚类聚合物。近年来利用木质素热解生产生物油已经得到许多关注。但利用微波热解木质素生成的固体产物(生物炭)来制备催化剂还鲜有报道。因此，本研究拟通过微波辅助热解制备木质素衍生生物炭，并在所生成的生物炭表面负载过渡金属氧元素以调节木质素衍生生物炭催化剂的理化性质，在微波热解木质素制备生物燃料过程中提高原料转化率，减少积炭的形成，提高催化剂的活性、选择性及使用寿命。 Biomass consists mainly of cellulose, hemicellulose and lignin. In woody plants, lignin accounts for 25% and is the second most abundant organic matter in the world (cellulose is the first). Lignin is a complex phenolic polymer formed from three alcohol monomers (coumaryl alcohol, coniferyl alcohol, sinapyl alcohol). In recent years, the production of bio-oil by lignin pyrolysis has received a lot of attention. However, it has rarely been reported that a solid product (biochar) produced by microwave pyrolysis of lignin is used to prepare a catalyst. Therefore, this study intends to prepare lignin-derived biochar by microwave-assisted pyrolysis and load transition metal oxygen on the surface of biochar produced to regulate the physicochemical properties of lignin-derived biochar catalyst. In the fuel process, the conversion rate of raw materials is increased, the formation of carbon deposits is reduced, and the activity, selectivity and service life of the catalyst are improved.
发明内容Summary of the invention
本发明的目的在于提供一种用于生产富芳烃生物燃油的催化剂及其制备方法，以得到改性后的催化剂，从而提高生物质催化热解反应中液体产率和品质，具体体现在提高原料转化率及生物油的化学组分选择性，减少催化剂积炭的形成，提高催化剂的活性及选择性。The object of the present invention is to provide a catalyst for producing an aromatic hydrocarbon-rich biofuel and a preparation method thereof, so as to obtain a modified catalyst, thereby improving liquid yield and quality in biomass catalytic pyrolysis reaction, specifically in improving raw materials. The conversion rate and the chemical component selectivity of the bio-oil reduce the formation of catalyst coke and increase the activity and selectivity of the catalyst.
为了解决上述技术问题，本发明以木质素微波热解衍生生物炭为催化剂载体原料，揭示负载过渡金属氧化物对所制备生物炭催化剂的影响，通过XRD、SEM等分析手段分析所制备的过渡金属改性生物炭催化剂微观形态变化、活性组分与载体的结合方式以及分布状态，具体技术方案如下：In order to solve the above technical problems, the present invention uses lignin microwave pyrolysis to derive biochar as a catalyst carrier raw material, reveals the influence of the supported transition metal oxide on the prepared biochar catalyst, and analyzes the prepared transition metal by XRD, SEM and other analytical means. The microscopic morphology of the modified biochar catalyst, the combination of the active component and the carrier, and the distribution state are as follows:
一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于包括以下步骤：A method for preparing a catalyst for producing an aromatic-rich biofuel, characterized by comprising the steps of:
步骤一，微波热解木质素获得生物炭；将木质素原料根据需用量称重并放置在石英烧瓶反应器内，将微波热解参数设定为反应温度500℃，微波功率为750W，为使木质素热解反应发生较完全，从而获得较纯净的生物炭，反应时间设定为30分钟；Step one, microwave pyrolysis of lignin to obtain biochar; the lignin raw material is weighed according to the required amount and placed in a quartz flask reactor, and the microwave pyrolysis parameter is set to a reaction temperature of 500 ° C, and the microwave power is 750 W, The lignin pyrolysis reaction occurs more completely, so that pure biochar is obtained, and the reaction time is set to 30 minutes;
步骤二，生物炭粉末的制备：将所述生物炭从石英烧瓶反应器中倒出并冷却至室温；由于木质素在微波热解时，容易形成粘结在一起块状生物炭产物。为了制备经过渡金属改性的生物炭催化剂，先要将微波热解生成的木质素衍生生物炭粉碎成细粉，然后筛分以确保尺寸的均匀性，从而获得生物炭粉末；Step 2: Preparation of biochar powder: The biochar is poured out from the quartz flask reactor and cooled to room temperature; since the lignin is pyrolyzed in the microwave, it is easy to form a block-like biochar product. In order to prepare a transition metal-modified biochar catalyst, the lignin-derived biochar produced by microwave pyrolysis is first pulverized into fine powder, and then sieved to ensure uniformity of size, thereby obtaining a biochar powder;
步骤三，用去离子水反复洗涤所述生物炭粉末，以从生物炭粉末结构中除去污染物并且打开生物炭表面孔，得纯净的生物炭粉末；Step three, repeatedly washing the biochar powder with deionized water to remove contaminants from the biochar powder structure and open the surface pores of the biochar to obtain pure biochar powder;
步骤四，将所述纯净的生物炭粉末在105℃的烘箱中干燥15h以除去多余水分，得干燥生物炭粉末；Step 4, drying the pure biochar powder in an oven at 105 ° C for 15 h to remove excess water to obtain a dried biochar powder;
步骤五，将称取好的锌盐溶于去离子水中，得到溶液A，在不断搅拌的情况下向溶液A中加入所述干燥生物炭粉末，得溶液B；所述锌盐中金属元素的质量比含量为所选择的生物炭的5％；Step 5, dissolving the weighed zinc salt in deionized water to obtain a solution A, and adding the dried biochar powder to the solution A under continuous stirring to obtain a solution B; the metal element in the zinc salt The mass ratio is 5% of the selected biochar;
步骤六，利用磁力搅拌器连续搅拌所述溶液B，得溶液C；Step six, using a magnetic stirrer to continuously stir the solution B, to obtain a solution C;
步骤七，对溶液C进行抽滤、成型，得成型的柱状颗粒物质，然后在烘箱中烘干，得产物一； Step 7, the solution C is subjected to suction filtration and molding to obtain a shaped columnar particulate material, which is then dried in an oven to obtain a product 1;
步骤八，在氮气和氢气的混合气氛围中通过高温管式炉对产物一进行焙烧，使其结晶、成型，从而制备得到最终产物，即改性后的负载有过渡金属的生物炭催化剂；所述混合气中氮气和氢气的体积比为99:1。Step 8: calcining the product one through a high-temperature tube furnace in a mixed gas atmosphere of nitrogen and hydrogen to crystallize and shape, thereby preparing a final product, that is, a modified biochar catalyst loaded with a transition metal; The volume ratio of nitrogen to hydrogen in the mixture is 99:1.
步骤一所述木质素原料为一种商业化木质素。The lignin raw material in the first step is a commercial lignin.
步骤五中所述锌盐为Zn(NO3)2.6H2O，锌盐与干燥生物炭粉末质量比为5％。The zinc salt in the fifth step is Zn(NO 3 ) 2 .6H 2 O, and the mass ratio of the zinc salt to the dried biochar powder is 5%.
步骤六具体为将溶液B放在磁力搅拌器上，在溶液中加入磁力搅拌子，在60℃的水浴中连续搅拌6h。Step 6 specifically, the solution B was placed on a magnetic stirrer, a magnetic stir bar was added to the solution, and stirring was continued for 6 hours in a water bath at 60 ° C.
所述步骤七具体为：抽滤、成型是在布氏漏斗中放一层滤纸然后将布氏漏斗连接真空泵，将溶液C在准备好的布氏漏斗中进行抽滤，抽滤完后保留滤纸上的残渣，然后使用塑料管将抽滤后的残渣制成直径5毫米、长7毫米的柱状颗粒，以方便做实验时使用。The step 7 is specifically: suction filtration, molding is to put a layer of filter paper in the Buchner funnel and then connect the Buchner funnel to the vacuum pump, and the solution C is suction filtered in the prepared Buchner funnel, and the filter paper is retained after the suction filtration. The residue was then made into a columnar particle having a diameter of 5 mm and a length of 7 mm using a plastic tube to facilitate use in experiments.
步骤七烘干条件具体为105℃的电烘箱中真空干燥15h。Step 7 The drying conditions were specifically vacuum dried in an electric oven at 105 ° C for 15 h.
所述步骤八中在管式炉内，用流速为60mL/min的混合气来维持缺氧气氛，以550℃的温度进行结晶4h。In the above-mentioned step 8, in a tube furnace, a mixed gas having a flow rate of 60 mL/min was used to maintain an oxygen-deficient atmosphere, and crystallization was performed at a temperature of 550 ° C for 4 hours.
一种用于生产富芳烃生物燃油的催化剂，其特征在于：利用上述方法制备而得。A catalyst for producing an aromatic-rich biofuel, which is produced by the above method.
本发明具有有益效果。本发明中制备的过渡金属改性后的生物炭催化剂，样品保持了生物炭拓扑结构的特征模式，经改性后的生物炭催化剂仍保持规整的结构形态。说明改性后的生物炭催化剂的分散性仍较好。以锌盐改性的生物炭的XRD图与没有改性的生物炭催化剂相比，它具有一个较为突出的峰，这是生成了由骨架物质之外物质所形成的高结晶，也表明该峰是由锌的加入引起的，而其他峰则与生物炭催化剂的峰一致。从SEM分析可以得到主要晶体颗粒及其附聚物在样品中随添加锌盐略有变化，与未添加金属的生物炭相比，经过加锌的样品的单晶尺寸稍有减小，且表面更为光滑。The present invention has a beneficial effect. The transition metal modified biochar catalyst prepared in the invention maintains the characteristic mode of the biochar topology, and the modified biochar catalyst still maintains a regular structure. It shows that the dispersibility of the modified biochar catalyst is still good. The XRD pattern of the biochar modified with zinc salt has a more prominent peak than the unmodified biochar catalyst, which is a high crystal formed by substances other than the framework material, and also indicates the peak. It is caused by the addition of zinc, while the other peaks are consistent with the peak of the biochar catalyst. From the SEM analysis, the main crystal particles and their agglomerates can be slightly changed in the sample with the addition of zinc salt. Compared with the biochar without metal addition, the single crystal size of the zinc-doped sample is slightly reduced, and the surface is slightly reduced. More smooth.
附图说明DRAWINGS
图1为本发明锌盐对改性生物炭催化剂的影响的XRD衍射图；Figure 1 is an XRD diffraction pattern of the effect of the zinc salt of the present invention on a modified biochar catalyst;
图2为本发明锌盐对改性生物炭催化剂的影响的SEM图；2 is an SEM image of the effect of the zinc salt of the present invention on a modified biochar catalyst;
图3为本发明加入改性后催化剂和未加催化剂木质素/PE微波共热解反应产物生物油组分分析图； 3 is an analysis diagram of the bio-oil component of the modified catalyst and the un-catalyzed lignin/PE microwave co-pyrolysis reaction product of the present invention;
图4为本发明的方法流程图。4 is a flow chart of a method of the present invention.
具体实施方式detailed description
下面结合附图和具体实施例，对本发明的技术方案做进一步详细说明。The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
实施例一Embodiment 1
本发明的方法流程图如图4所示。将40g木质素生物质原料称重并放置在反应烧瓶内，不加入加热剂，使得所得的焦炭尽可能纯。实验开始前通入氮气15min以保持无氧的氛围。将微波热解参数设定为反应温度500℃，微波功率为750W，为使木质素热解反应发生较完全，从而获得较纯净的生物炭，反应时间设定为30分钟。由于木质素在微波热解时，容易形成粘结在一起块状生物炭产物。为了制备经过渡金属改性的生物炭催化剂，先要将微波热解生成的木质素衍生生物炭粉碎成细粉，然后筛分以确保尺寸的均匀性。然后，用去离子水反复洗涤生物炭粉末。洗涤后，在105℃的烘箱中干燥15h以除去多余水分。这就得到了制备催化剂的生物炭原料。将称取好的10.13g的Zn(NO3)2.6H2O溶于过量去离子水中，在不断搅拌的情况下向其中加入生物炭原料40g。将溶液放在磁力搅拌器上，在60℃的水浴中连续搅拌6h。抽滤、成型，将成型的物质在105℃的电烘箱中真空干燥15h。然后以流速为60mL/min的氮气氢气混合气氛(99:1)来维持缺氧气氛，以550℃的温度进行结晶4h，制成负载金属锌的生物炭催化剂。为了对比金属锌改性后的催化剂和未经处理的催化剂的晶体特征进行了XRD表征，如图1所示。改性后的分子筛催化剂保持了原催化剂的拓扑结构的特征模式，但出现一个由金属锌加入形成的突出峰，说明改性后的金属锌负载到了生物炭催化剂中。如图2所示的负载锌的生物炭催化剂和生物炭催化剂的SEM对比图。说明负载金属锌的催化剂的单晶尺寸稍有减小，且表面更为光滑。A flowchart of the method of the present invention is shown in FIG. 40 g of the lignin biomass feedstock was weighed and placed in the reaction flask without the addition of a heating agent, so that the resulting coke was as pure as possible. Nitrogen gas was introduced for 15 min before the start of the experiment to maintain an oxygen-free atmosphere. The microwave pyrolysis parameter was set to a reaction temperature of 500 ° C and a microwave power of 750 W. In order to make the lignin pyrolysis reaction more complete, a relatively pure biochar was obtained, and the reaction time was set to 30 minutes. Since lignin is pyrolyzed in the microwave, it is easy to form a block-like biochar product. In order to prepare a transition metal-modified biochar catalyst, the lignin-derived biochar produced by microwave pyrolysis is first pulverized into fine powder and then sieved to ensure uniformity of size. Then, the biochar powder was repeatedly washed with deionized water. After washing, it was dried in an oven at 105 ° C for 15 h to remove excess water. This gave a biochar raw material for the preparation of the catalyst. The weighed 10.13 g of Zn(NO 3 ) 2 .6H 2 O was dissolved in excess deionized water, and 40 g of a biochar raw material was added thereto with constant stirring. The solution was placed on a magnetic stirrer and continuously stirred in a water bath at 60 ° C for 6 h. The mixture was filtered, molded, and the formed material was vacuum dried in an electric oven at 105 ° C for 15 h. Then, an oxygen-deficient atmosphere was maintained at a flow rate of 60 mL/min in a nitrogen-hydrogen mixed atmosphere (99:1), and crystallization was carried out at a temperature of 550 ° C for 4 hours to prepare a metal-supported biochar catalyst. XRD characterization was performed to compare the crystal characteristics of the metal zinc modified catalyst and the untreated catalyst, as shown in FIG. The modified molecular sieve catalyst maintains the characteristic pattern of the topological structure of the procatalyst, but a prominent peak formed by the addition of metallic zinc appears, indicating that the modified metallic zinc is loaded into the biochar catalyst. A SEM comparison of the zinc-loaded biochar catalyst and biochar catalyst as shown in FIG. It is indicated that the single crystal size of the catalyst supporting the metal zinc is slightly reduced and the surface is smoother.
实施例二Embodiment 2
为了验证所改性后的催化剂对生物质热解转化的影响，采用催化固定床反应器与微波热解装置联用进行了催化热解实验。试验所用的原料为木质素：首先称取20g的木质素和5g的PE作为原料放于容量为500ml的石英烧瓶反应器中，然后加入1g的活性炭作为微波吸收材料与木质素/聚乙烯(PE)混合，再将石英烧瓶反应器置于微波炉中，在催化固定床反应器中放置1g的所制备的催化剂。设置微波热解的反应温度为500℃，时间为8min，微波功率为750W；热解气通过微波热解反应后经过催化固定床进行催化重整反应，再经快速冷凝后 收集生物油，收集反应后的生物油有机组分及催化剂经GC/MS、SEM、XRD等表征手段进行分析。试验中对比了未添加催化剂与添加金属锌改性后生物炭催化剂的微波热解实验，发现使用催化剂明显比未加催化剂获得的生物油多，催化剂对生物油产率的影响为：锌-生物炭催化剂>无催化剂。催化剂对合成气产率的影响与它对生物油产率的影响一致。发现添加催化剂可以获得更多的生物燃油。由GC/MS分析微波共热解木质素、木质素/PE以及木质素/PE+锌-生物炭所得到的生物油的组分分析图，如图3所示，它的主要化学化合物是醛/酮、酚类、有机酸、醇、糖、酯及烃。其中添加锌-生物炭催化剂与其他两个相比，有机酸的含量明显降低了(由5.23％降到0％)，并且它富芳烃的含量所占比例最多，高达49％，而木质素/PE富芳烃的含量为23.33％，木质素富芳烃的含量几乎为零。说明锌-生物炭催化剂的使用提高了生物油的中芳烃的选择性和生物油的品质，可用于生产富芳烃生物燃油。 In order to verify the effect of the modified catalyst on biomass pyrolysis conversion, a catalytic pyrolysis experiment was carried out by using a catalytic fixed bed reactor in combination with a microwave pyrolysis apparatus. The raw material used in the test was lignin: firstly weighed 20 g of lignin and 5 g of PE as raw materials in a quartz flask reactor with a capacity of 500 ml, and then added 1 g of activated carbon as a microwave absorbing material and lignin/polyethylene (PE). The mixture was mixed, and the quartz flask reactor was placed in a microwave oven, and 1 g of the prepared catalyst was placed in a catalytic fixed bed reactor. The reaction temperature for setting microwave pyrolysis is 500 ° C, the time is 8 min, and the microwave power is 750 W. The pyrolysis gas is subjected to catalytic reforming reaction through a catalytic fixed bed after microwave pyrolysis reaction, and then rapidly condensed. The bio-oil was collected, and the organic components and catalysts of the bio-oil after the reaction were collected and analyzed by means of GC/MS, SEM and XRD. In the experiment, the microwave pyrolysis experiments of the uncharged catalyst and the added metal zinc modified biochar catalyst were compared. It was found that the catalyst used was significantly more than the bio-oil obtained without the catalyst. The effect of the catalyst on the bio-oil yield was: zinc-bio Carbon catalyst > no catalyst. The effect of the catalyst on the yield of syngas is consistent with its effect on the yield of bio-oil. It was found that adding biocatalyst could result in more biofuel. The composition analysis of bio-oil obtained by microwave co-pyrolysis of lignin, lignin/PE and lignin/PE+zinc-biochar by GC/MS, as shown in Fig. 3, its main chemical compound is aldehyde/ Ketones, phenols, organic acids, alcohols, sugars, esters and hydrocarbons. Compared with the other two, the addition of zinc-biochar catalysts significantly reduced the content of organic acids (from 5.23% to 0%), and its aromatic-rich content accounted for the most, up to 49%, while lignin/ The content of PE-rich aromatic hydrocarbons is 23.33%, and the content of lignin-rich aromatic hydrocarbons is almost zero. It is indicated that the use of zinc-biochar catalysts improves the selectivity of aromatic hydrocarbons in bio-oil and the quality of bio-oil, and can be used to produce aromatic-rich biofuels.

Claims (8)

  1. 一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于包括以下步骤：A method for preparing a catalyst for producing an aromatic-rich biofuel, characterized by comprising the steps of:
    步骤一，微波热解木质素获得生物炭；将木质素原料根据需用量称重并放置在石英烧瓶反应器内，将微波热解参数设定为反应温度500℃，微波功率为750W，为使木质素热解反应发生较完全，从而获得较纯净的生物炭，反应时间设定为30分钟；Step one, microwave pyrolysis of lignin to obtain biochar; the lignin raw material is weighed according to the required amount and placed in a quartz flask reactor, and the microwave pyrolysis parameter is set to a reaction temperature of 500 ° C, and the microwave power is 750 W, The lignin pyrolysis reaction occurs more completely, so that pure biochar is obtained, and the reaction time is set to 30 minutes;
    步骤二，生物炭粉末的制备：将所述生物炭从石英烧瓶反应器中倒出并冷却至室温；由于木质素在微波热解时，容易形成粘结在一起块状生物炭产物。为了制备经过渡金属改性的生物炭催化剂，先要将微波热解生成的木质素衍生生物炭粉碎成细粉，然后筛分以确保尺寸的均匀性，从而获得生物炭粉末；Step 2: Preparation of biochar powder: The biochar is poured out from the quartz flask reactor and cooled to room temperature; since the lignin is pyrolyzed in the microwave, it is easy to form a block-like biochar product. In order to prepare a transition metal-modified biochar catalyst, the lignin-derived biochar produced by microwave pyrolysis is first pulverized into fine powder, and then sieved to ensure uniformity of size, thereby obtaining a biochar powder;
    步骤三，用去离子水反复洗涤所述生物炭粉末，以从生物炭粉末结构中除去污染物并且打开生物炭表面孔，得纯净的生物炭粉末；Step three, repeatedly washing the biochar powder with deionized water to remove contaminants from the biochar powder structure and open the surface pores of the biochar to obtain pure biochar powder;
    步骤四，将所述纯净的生物炭粉末在105℃的烘箱中干燥15h以除去多余水分，得干燥生物炭粉末；Step 4, drying the pure biochar powder in an oven at 105 ° C for 15 h to remove excess water to obtain a dried biochar powder;
    步骤五，将称取好的锌盐溶于去离子水中，得到溶液A，在不断搅拌的情况下向溶液A中加入所述干燥生物炭粉末，得溶液B；所述锌盐中金属元素的质量比含量为所选择的生物炭的5％；Step 5, dissolving the weighed zinc salt in deionized water to obtain a solution A, and adding the dried biochar powder to the solution A under continuous stirring to obtain a solution B; the metal element in the zinc salt The mass ratio is 5% of the selected biochar;
    步骤六，利用磁力搅拌器连续搅拌所述溶液B，得溶液C；Step six, using a magnetic stirrer to continuously stir the solution B, to obtain a solution C;
    步骤七，对溶液C进行抽滤、成型，得成型的柱状颗粒物质，然后在烘箱中烘干，得产物一；Step 7, the solution C is subjected to suction filtration and molding to obtain a shaped columnar particulate material, which is then dried in an oven to obtain a product 1;
    步骤八，在氮气和氢气的混合气氛围中通过高温管式炉对产物一进行焙烧，使其结晶、成型，从而制备得到最终产物，即改性后的负载有过渡金属的生物炭催化剂；所述混合气中氮气和氢气的体积比为99:1。Step 8: calcining the product one through a high-temperature tube furnace in a mixed gas atmosphere of nitrogen and hydrogen to crystallize and shape, thereby preparing a final product, that is, a modified biochar catalyst loaded with a transition metal; The volume ratio of nitrogen to hydrogen in the mixture is 99:1.
  2. 根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于：步骤一所述木质素原料为一种商业化木质素。The method for preparing a catalyst for producing an aromatic-rich biofuel according to claim 1, wherein in the first step, the lignin raw material is a commercial lignin.
  3. 根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于：步骤五中所述锌盐为Zn(NO3)2.6H2O，锌盐与干燥生物炭粉末 质量比为5％。The method for preparing a catalyst for producing an aromatic-rich biofuel according to claim 1, wherein the zinc salt in the fifth step is Zn(NO 3 ) 2 .6H 2 O, a zinc salt and a dry organism. The mass ratio of the carbon powder was 5%.
  4. 根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于：步骤六具体为将溶液B放在磁力搅拌器上，在溶液中加入磁力搅拌子，在60℃的水浴中连续搅拌6h。The method for preparing a catalyst for producing an aromatic-rich biofuel according to claim 1, wherein the step 6 is specifically: placing the solution B on a magnetic stirrer, and adding a magnetic stirrer to the solution, at 60 Stirring was continued for 6 h in a water bath at °C.
  5. 根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于所述步骤七具体为：抽滤、成型是在布氏漏斗中放一层滤纸然后将布氏漏斗连接真空泵，将溶液C在准备好的布氏漏斗中进行抽滤，抽滤完后保留滤纸上的残渣，然后使用塑料管将抽滤后的残渣制成直径5毫米、长7毫米的柱状颗粒，以方便做实验时使用。The method for preparing a catalyst for producing an aromatic-rich biofuel according to claim 1, wherein the step 7 is specifically: suction filtration, molding is to put a layer of filter paper in a Buchner funnel and then Brinell. The funnel is connected to the vacuum pump, and the solution C is suction-filtered in the prepared Buchner funnel. After the filtration, the residue on the filter paper is retained, and then the filtered residue is made into a column having a diameter of 5 mm and a length of 7 mm by using a plastic tube. Granules are used for ease of experimentation.
  6. 根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于：步骤七烘干条件具体为105℃的电烘箱中真空干燥15h。The method for preparing a catalyst for producing an aromatic-rich biofuel according to claim 1, characterized in that the drying condition of the step 7 is specifically vacuum drying in an electric oven at 105 ° C for 15 h.
  7. 根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法，其特征在于：所述步骤八中在管式炉内，用流速为60mL/min的混合气来维持缺氧气氛，以550℃的温度进行结晶4h。A method for preparing a catalyst for producing an aromatic-rich biofuel according to claim 1, wherein in the step eight, a mixture of a flow rate of 60 mL/min is used to maintain anoxic in a tube furnace. The atmosphere was crystallized at a temperature of 550 ° C for 4 h.
  8. 一种用于生产富芳烃生物燃油的催化剂，其特征在于：利用权利要求1-6中任一权利要求的方法制备而得。 A catalyst for producing an aromatic-rich biofuel, which is produced by the method of any of claims 1-6.
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