CN110129084B - Biomass hydrogen supply-catalytic liquefaction coupling method and supported biomass liquefaction catalyst - Google Patents

Biomass hydrogen supply-catalytic liquefaction coupling method and supported biomass liquefaction catalyst Download PDF

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CN110129084B
CN110129084B CN201910457900.1A CN201910457900A CN110129084B CN 110129084 B CN110129084 B CN 110129084B CN 201910457900 A CN201910457900 A CN 201910457900A CN 110129084 B CN110129084 B CN 110129084B
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biomass
liquefaction
catalyst
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hydrogen supply
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CN110129084A (en
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宋林花
黄仕能
李志恒
胡明明
阎子峰
刘�东
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China University of Petroleum East China
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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
    • B01J23/70—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
    • B01J23/75—Cobalt
    • 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—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
    • 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

Abstract

The invention relates to the technical field of biomass liquefaction, and provides a biomass hydrogen supply-catalytic liquefaction coupling method, which comprises the following steps: mixing the biomass powder, a hydrogen donor solvent and a supported biomass liquefaction catalyst for liquefaction reaction to obtain a liquid-phase product. The invention couples catalytic liquefaction and hydrogen supply liquefaction, fully utilizes the synergistic effect between the hydrogen supply agent and the catalyst, realizes the high-efficiency conversion of biomass, improves the heat value of a liquid-phase product, improves the liquid-phase yield, and overcomes the defects of high hydrogen consumption, low bio-oil yield and the like of a single process. The invention also provides a supported biomass liquefaction catalyst which has the effects of catalytic cracking and activity of promoting free radical transfer, is more environment-friendly compared with a liquid homogeneous catalyst, is easy to separate and recover, is applied to a biomass hydrogen supply-catalytic liquefaction coupling process, and can realize efficient liquefaction and conversion of biomass.

Description

Biomass hydrogen supply-catalytic liquefaction coupling method and supported biomass liquefaction catalyst
Technical Field
The invention relates to the technical field of biomass liquefaction, in particular to a biomass hydrogen supply-catalytic liquefaction coupling method and a supported biomass liquefaction catalyst.
Background
In the energy structure of the world, fossil fuels still dominate nowadays, but the energy shortage and environmental pollution caused by the rapid consumption of coal, petroleum, natural gas and the like are becoming serious, and the development and application of novel clean energy are urgent. Biomass energy is a renewable clean energy source, which is derived from photosynthesis of plants and contains less nitrogen, sulfur and heavy metals than fossil energy sources. Therefore, techniques for efficient conversion and utilization of biomass have received much attention.
The thermochemical conversion of biomass has been widely studied because of its high energy utilization and short conversion cycle, and is more suitable for large-scale production in industry. Wherein, the liquefaction technology of the biomass can convert low-grade solid biomass into liquid bio-oil with high added value, and is an effective way for efficiently utilizing biomass energy, relieving energy pressure and protecting environment.
The liquefaction reaction process of the biomass comprises hydrogenation liquefaction, hydrogen supply liquefaction and catalytic liquefaction. The hydro-liquefaction reaction is carried out under an atmosphere of hydrogen gas, aiming at reducing the oxygen content in the bio-oil. Patent CN 103509578A discloses a process for preparing biomass fuel by hydrogenating and liquefying corn stalks, which liquefies crushed corn stalks into bio-oil at high temperature and high pressure in a hydrogen atmosphere, and has relatively harsh reaction conditions and high hydrogen consumption. In contrast, the hydrogen supply liquefaction reaction is carried out in a solvent rich in active hydrogen, and the hydrogen supply agent can provide active hydrogen radicals for the reaction, stabilize an intermediate generated by the liquefaction reaction and promote the liquefaction conversion of the raw material; and simultaneously, the condensation and polymerization of the intermediate can be inhibited, and the generation amount of coke can be reduced. For example, a biomass hydrogen-donating pyrolysis process in the presence of naphthenic base petroleum hydrogen-donating distillate oil related in patent CN 103254923A.
The catalytic liquefaction of the biomass is to catalyze the liquefaction reaction of the biomass by using a catalyst under an inert atmosphere. Homogeneous or heterogeneous acid-base catalysts are widely used in catalytic liquefaction reactions of biomass, and aim to improve the conversion rate of raw materials or the selectivity of products. For example, patent CN 101407727 adopts solid acid (active clay, acidic metal oxide and solid super acid) to catalyze and liquefy biomass, and the use of the catalyst obviously improves the yield of bio-oil.
Catalysts in biomass liquefaction can be divided into two categories, homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts mainly comprise acid and base catalysts (such as H)2SO4、HCl、H3PO4And KOH,NaOH、 Na2CO3Etc.), but the acid-base catalyst has serious corrosion to the reactor, needs neutralization treatment subsequently and has the problem of difficult separation and recovery; in contrast, heterogeneous catalysts are more environmentally friendly, such as supported catalysts. Porous carriers, such as supported catalysts of carbon materials, metal oxides, molecular sieves, etc., are widely used in reactions of catalytic liquefaction of biomass, for example, patent CN 105251524 a, CN 108499598A, etc., and these catalysts significantly improve the quality or selectivity of products.
However, the liquefaction yield of biomass is still low in the current liquefaction method, and no research is currently conducted on coupling catalytic liquefaction and hydrogen supply liquefaction.
Disclosure of Invention
In view of the above, the present invention aims to provide a biomass hydrogen co-supply-catalytic liquefaction coupling method and a supported biomass liquefaction catalyst. According to the invention, the biomass is treated by utilizing the supported biomass liquefaction catalyst in the hydrogen donor solvent, the biomass hydrogen donor liquefaction and the biomass catalytic liquefaction are combined together, the synergistic effect between the hydrogen donor and the catalyst is fully utilized, the biomass liquefaction conversion is effectively promoted, and a new thought is provided for biomass liquefaction.
In order to achieve the above object, the present invention provides the following technical solutions:
a biomass hydrogen supply-catalytic liquefaction coupling method comprises the following steps:
mixing the biomass powder, a hydrogen donor solvent and a supported biomass liquefaction catalyst for liquefaction reaction to obtain a liquid-phase product.
Preferably, the raw material of the biomass powder is one or more of wood chips, algae, crop straws and nut shells;
the particle size of the biomass powder is 40-100 meshes.
Preferably, the solid-liquid ratio of the biomass powder to the hydrogen donor solvent is 1: 2-10 g/mL; the mass content of the supported biomass liquefaction catalyst in the slurry obtained by mixing is 2-10%.
Preferably, the temperature of the liquefaction reaction is 280-360 ℃, and the time is 20-60 min; the liquefaction reaction is carried out under an inert atmosphere.
Preferably, the hydrogen donor solvent comprises one or more of alpha-H-containing alcohol, active hydrogen-containing alkane, active hydrogen-containing aromatic hydrocarbon or distillate oil.
Preferably, the supported biomass liquefaction catalyst comprises a carrier and an active center supported on the carrier; the carrier is a porous material; the active center is Ni and/or Fe; the loading amount of the active center in the catalyst is 2-10 wt.%.
Preferably, the catalyst also comprises an auxiliary agent loaded on a carrier; the auxiliary agent comprises one or more of Cu, Co, Mo and Ag; the loading amount of the auxiliary agent in the catalyst is 0.5-2.5 wt.%.
Preferably, the porous material comprises activated carbon, gamma-Al2O3One or more of HZSM-5, MCM-41 and porous magnesium oxide.
Preferably, the preparation method of the porous magnesium oxide comprises the following steps:
and mixing the magnesium salt solution and the precipitant solution for aging, and drying and roasting the aged product in sequence to obtain the porous magnesium oxide.
The invention also provides a supported biomass liquefaction catalyst, which comprises a carrier and an active center loaded on the carrier; the carrier is a porous material; the active center is Ni and/or Fe; the loading amount of the active center in the catalyst is 2-10 wt.%.
The invention provides a biomass hydrogen supply-catalytic liquefaction coupling method, which comprises the following steps: mixing the biomass powder, a hydrogen donor solvent and a supported biomass liquefaction catalyst for liquefaction reaction to obtain a liquid-phase product. According to the invention, the biomass is treated by utilizing the supported biomass liquefaction catalyst in the hydrogen supply solvent, so that the high-efficiency liquefaction and conversion of the biomass are realized; the invention couples the catalytic liquefaction of the catalyst with the hydrogen supply liquefaction of the hydrogen supply solvent, and effectively blocks unstable biomass cracking by utilizing active hydrogen provided by the hydrogen supply agent while the biomass is efficiently catalytically cracked by the supported biomass liquefaction catalystThe condensation and polymerization reaction of the intermediate are carried out, so that the conversion rate of the biomass raw material and the yield of liquid-phase products are improved, and the yield of solid coke is reduced; in addition, the oxygen content of the bio-oil product is effectively reduced due to the existence of active hydrogen in the reaction system, so that the heat value of the liquid-phase target product is improved; the invention fully utilizes the synergistic effect between the hydrogen donor and the catalyst, overcomes the defects of high hydrogen consumption, low bio-oil yield and the like of the traditional single process, and the used supported biomass liquefaction catalyst is easy to separate and recover and is more environment-friendly. The results of the examples show that the conversion of the raw material can reach 80%, the liquid phase yield of the product can reach 64.7%, and the heat value of the liquid phase product can reach 33.04 MJ.kg when the biomass is liquefied by using the method of the invention-1。
The invention also provides a supported biomass liquefaction catalyst which has the effects of catalytic cracking and activity of promoting free radical transfer, belongs to a heterogeneous catalyst, is more environment-friendly and easy to separate and recover compared with a liquid homogeneous catalyst, and can be applied to a biomass hydrogen supply-catalytic liquefaction coupling process to realize efficient liquefaction and conversion of biomass.
Drawings
FIG. 1 is a schematic diagram of an apparatus for coupling hydrogen supply to catalytic liquefaction of biomass according to the present invention;
in fig. 1: 1-water tank, 2-dryer, 3-pulverizer, 4-standard sieve, 5-mixing barrel, 6-slurry feeding pump, 7-high pressure reactor, 8-gas flowmeter, 9-gas chromatography, 10-solid-liquid separation device and 11 product tank.
Detailed Description
The invention provides a biomass hydrogen supply-catalytic liquefaction coupling method, which comprises the following steps:
mixing the biomass powder, a hydrogen donor solvent and a supported biomass liquefaction catalyst for liquefaction reaction to obtain a liquid-phase product.
In the invention, the raw material of the biomass powder is preferably one or more of wood chips, algae, crop straws and nut shells; the algae is preferably enteromorpha; the granularity of the biomass powder is preferably 40-100 meshes, and more preferably 50-80 meshes; in the present invention, the biomass powder is preferably prepared by the following steps: sequentially washing, drying, crushing and screening the biomass raw material to obtain biomass powder; the invention has no special requirements on the specific conditions of washing, drying, crushing and screening, and can obtain the biomass powder with the required granularity.
In the invention, the hydrogen-donor solvent preferably comprises one or more of alcohol containing alpha-H, alkane containing active hydrogen, aromatic hydrocarbon containing active hydrogen or distillate oil; the alpha-H containing alcohol preferably comprises one or more of ethanol, isopropanol and cyclohexanol; the active hydrogen-containing alkane preferably comprises cyclohexane; the active hydrogen-containing aromatic hydrocarbon preferably includes tetrahydronaphthalene. In the invention, the hydrogen donor solvent is rich in active hydrogen, and can provide active hydrogen radicals for the liquefaction reaction of the biomass and promote the liquefaction conversion of the biomass.
In the present invention, the supported biomass liquefaction catalyst preferably includes a carrier and an active center supported on the carrier; the support is preferably a porous material; the active center is preferably Ni and/or Fe; the loading amount of the active center in the catalyst is preferably 2-10 wt%, more preferably 3-8 wt%, and further preferably 4-6 wt%.
In the present invention, the porous material preferably includes activated carbon, γ -Al2O3One or more of HZSM-5, MCM-41 and porous magnesia, more preferably activated carbon or porous magnesia, and most preferably porous magnesia; the invention is to the activated carbon, gamma-Al2O3The source of HZSM-5 and MCM-41 is not particularly limited, and commercially available materials as described above may be used.
In the present invention, the porous magnesium oxide is preferably prepared by itself, and the preparation method of the porous magnesium oxide preferably includes the steps of:
and mixing the magnesium salt solution and the precipitant solution for aging, and drying, roasting and forming the aged product in sequence to obtain the porous magnesium oxide.
In the present invention, the magnesium salt preferably comprises Mg (CH)3COO)3·4H2O and/or MgCl2·6H2O; the solvent of the magnesium salt solution is preferably deionized water; the concentration of the magnesium salt solution is preferably 0.02-0.06 mol/L, and more preferably 0.04 mol/L; the precipitating agent is preferably H2C2O4·4H2O， (NH4)2C2O4·H2One or more of O and anhydrous sodium carbonate; the solvent of the precipitant solution is preferably water; the concentration of the precipitant solution is preferably 0.04-0.08 mol/L, and more preferably 0.06 mol/L; in the invention, the magnesium salt solution is preferably added into the precipitator solution dropwise, and the aging is carried out after the dropwise addition is finished.
In the invention, the aging temperature is preferably 30-60 ℃, and more preferably 40-50 ℃; the aging time is preferably 6-12 h, and more preferably 8-10 h. In the invention, during the aging process, magnesium ions react with a precipitator to generate magnesium oxide precursor precipitate.
After the aging is finished, the aging liquid is preferably filtered, the filter cake is washed to be neutral to obtain an aging product, and then the aging product is sequentially dried and roasted to obtain the porous magnesium oxide. In the invention, the drying temperature is preferably 110 ℃, and the drying time is preferably 4 hours; the roasting temperature is preferably 400-800 ℃, and more preferably 500-700 ℃; the roasting time is preferably 2-5 h, and more preferably 3-5 h; the calcination is preferably carried out under a nitrogen atmosphere. N in the course of calcination2The water vapor and carbon dioxide generated by roasting are taken away in time, and the sintering of the magnesium oxide crystal grains is prevented.
After completion of the calcination, the present invention also preferably includes press-forming the porous magnesium oxide powder obtained by the calcination. The present invention has no special requirement on the specific method of the compression molding, and the method known by the technicians in the field can be used, in the specific embodiment of the present invention, the porous magnesium oxide can be compressed into strips, blocks, etc., the size of the dimension in the compression molding process, the dosage of the required adhesive, the type of the adhesive, etc. can be determined according to the specific production conditions, and the present invention is not particularly limited; the porous magnesium oxide can be more suitable for industrialization by compression molding.
The specific surface area of the pores of the porous magnesium oxide prepared by the method is 86.54-203.51 m2(iv)/g, the average pore diameter is 5.68-26.58 nm.
In the present invention, the supported biomass liquefaction catalyst preferably further comprises an auxiliary agent supported on a carrier; the auxiliary agent is preferably one or more of Cu, Co, Mo and Ag; the loading amount of the auxiliary agent in the catalyst is preferably 0.5-2.5 wt.%, more preferably 1-2 wt.%, and even more preferably 1.5 wt.%.
In the invention, the preparation method of the supported biomass liquefaction catalyst is preferably an isometric impregnation method, and specifically comprises the following steps:
and (3) dipping the carrier in an active center precursor solution, and drying, reducing and roasting the dipped carrier in sequence to obtain the supported biomass liquefaction catalyst.
In the present invention, the active center precursor preferably includes Ni (NO)3)2·6H2O and/or Fe (NO)3)3·9H2O; the temperature of the impregnation is preferably room temperature, and the time is preferably 24 h; the drying temperature is preferably 120 ℃, and the drying time is preferably 8 h; the temperature of the reduction roasting is preferably 400-800 ℃, more preferably 500-700 ℃, and the time of the reduction roasting is preferably 3-6 hours, more preferably 4-5 hours; the reduction roasting is preferably carried out at 95% Ar-5% H2The preparation is carried out in mixed atmosphere; in the reduction roasting process, the active center precursor loaded on the carrier is reduced into Ni or Fe simple substance.
In the invention, when the supported biomass liquefaction catalyst further comprises an auxiliary agent, the auxiliary agent precursor is preferably added into the impregnation liquid, and the subsequent operation steps and the operation conditions are consistent with the scheme, and are not described again; the promoter precursor preferably comprises Cu (NO)3)2·3H2O、 Co(NO3)2·6H2O、(NH4)6Mo7O24·4H2O、AgNO3And Ce (NO)3)3·6H2One or more of O; in the specific embodiment of the invention, the concentrations of the active center precursor and the auxiliary agent precursor in the impregnation liquid are determined according to the water absorption capacity of the carrier by the equal volume impregnation method.
According to the invention, biomass powder, a hydrogen donor solvent and a catalyst are mixed for carrying out liquefaction reaction, wherein the solid-to-liquid ratio of the biomass powder to the hydrogen donor solvent is preferably 1: 2-10 g/mL, and more preferably 1: 4-8 g/mL; the mass content of the catalyst in the slurry obtained by mixing is preferably 2-10%, more preferably 3-8%, and most preferably 4-5%.
In the invention, the temperature of the liquefaction reaction is preferably 280-360 ℃, more preferably 300-340 ℃, and further preferably 320-330 ℃; the time of the liquefaction reaction is preferably 20-60 min, and more preferably 30-50 min; the liquefaction reaction is preferably carried out under an inert atmosphere; in the embodiment of the invention, preferably, the slurry obtained by mixing is pumped into a high-pressure reaction kettle, then the reaction kettle is purged by high-purity nitrogen to discharge air, and the mixture is stirred and heated to the liquefaction reaction temperature under the condition of no pressurization; the biomass is subjected to hydrogen supply liquefaction and catalytic liquefaction simultaneously in a closed reaction kettle, and active hydrogen provided by a hydrogen supply solvent can effectively block condensation and polymerization reactions of biomass cracking unstable intermediates while the biomass is subjected to high-efficiency catalytic cracking by a catalyst, so that the conversion rate and the liquid-phase yield of the biomass raw material are improved, the oxygen content of a liquid-phase product is reduced, and the heat value of the bio-oil (namely the liquid-phase product) is improved; in addition, under the high-temperature closed condition, the biomass can generate gas and solid coke besides liquid products, in the specific embodiment of the invention, preferably, a gas flowmeter is used for measuring the gas volume after the liquefaction reaction is finished, then gas composition is analyzed on line by adopting gas chromatography, gas phase yield is calculated, solid-liquid phase products in a reaction kettle are subjected to solid-liquid separation, the obtained liquid phase product is biological oil, the solid phase product (the mixture of the solid coke and the catalyst) is washed by acetone and then dried to constant weight, and the biomass conversion rate and the liquid phase yield are calculated according to the gas phase yield and the mass of the solid phase product; in the invention, the catalyst is a supported catalyst, the catalyst is not mixed with a liquid phase product after solid-liquid separation, the problem that a homogeneous catalyst is difficult to separate can be avoided, the catalyst used in the invention contains magnetic Ni or Fe, and after a solid phase product is dried, the catalyst is recovered by using a strong magnetic magnet.
In the specific embodiment of the present invention, the coupling of hydrogen supply and catalytic liquefaction of biomass is preferably realized by using the apparatus shown in fig. 1, which includes a water tank 1, a dryer 2, a pulverizer 3, a standard sieve 4, a mixing barrel 5, a slurry feed pump 6, a high-pressure reaction kettle 7, a gas flow meter 8, a gas chromatograph 9, a solid-liquid separation apparatus 10 and a product tank 11; in the specific embodiment of the invention, biomass is cleaned in a water tank 1, dried in a dryer 2, then crushed in a crusher 3, crushed material is sieved in a standard sieve 4 to obtain biomass powder, the biomass powder, a hydrogen supply solvent and a supported biomass liquefaction catalyst are mixed in a mixing barrel 5 and then pumped into a high-pressure reaction kettle 7 by a slurry feed pump 6 for hydrogen supply-catalytic liquefaction, a gas flowmeter 8 is used for measuring the gas volume after the reaction is finished, and gas composition is analyzed by gas chromatography; meanwhile, solid-liquid phase products in the reaction kettle are separated through a solid-liquid separation device 10, and liquid phase products (bio-oil) enter a product tank 11 for storage.
The invention also provides a supported biomass liquefaction catalyst, which comprises a carrier and an active center loaded on the carrier; the carrier is a porous material; the active center is Ni and/or Fe; the loading amount of the active center in the catalyst is 2-10 wt.%, preferably 3-8 wt.%, and further preferably 4-6 wt.%; the supported biomass liquefaction catalyst preferably further comprises an auxiliary agent supported on a carrier; the auxiliary agent is preferably one or more of Cu, Co, Mo and Ag; the loading amount of the auxiliary agent in the catalyst is preferably 0.5-2.5 wt.%, more preferably 1-2 wt.%, and even more preferably 1.5 wt.%.
In the invention, the types of the carriers and the preparation method of the supported biomass liquefaction catalyst are consistent with the scheme, and are not described again; the supported biomass liquefaction catalyst provided by the invention has the effects of catalytic cracking and activity of promoting free radical transfer, is easy to separate and recover, and can be applied to a biomass hydrogen supply-catalytic liquefaction coupling process to realize efficient liquefaction and conversion of biomass.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing a supported biomass liquefaction catalyst by adopting an isometric impregnation method:
(1) preparation of 10% Fe/MgO catalyst
50mL of 0.04mol/L MgCl2·6H2O solution was added dropwise to 200mL of 0.06mol/L H2C2O4·4H2Adding O solution, aging at 30 deg.C for 6 hr, filtering and washing the aged product to neutral, drying at 110 deg.C for 4 hr, and adding N2Roasting for 3h at 400 ℃ in the atmosphere to obtain the porous magnesium oxide.
Porous magnesium oxide in Fe (NO)3)3·9H2Soaking in O solution for 24 hr, taking out the soaked porous magnesium oxide, drying at 120 deg.C for 8 hr, and soaking in 95% Ar-5% H2And carrying out reduction roasting for 3h at 400 ℃ in a mixed atmosphere to obtain the supported biomass liquefaction catalyst, wherein the carrier is porous magnesium oxide, the active center is Fe, and the loading amount of Fe is 10 wt%, which is recorded as 10% Fe/MgO.
(2) Preparation of 10% Ni/AC catalyst
Adding activated carbon to Ni (NO)3)3·6H2Soaking in O solution for 24 hr, taking out the soaked activated carbon, drying at 120 deg.C for 8 hr, and soaking in 95% Ar-5% H2And carrying out reduction roasting for 4h at 500 ℃ in a mixed atmosphere to obtain the supported biomass liquefaction catalyst, wherein the carrier is activated carbon, the active center is Ni, and the loading amount of Ni is 10 wt%, which is recorded as 10% Ni/AC.
(3) Preparation of 10% Ni-2.5% Co/AC catalyst
Adding activated carbon to Ni (NO)3)3·6H2O and Co (NO)3)3·6H2Soaking in the mixed solution of O for 24 hours; taking out the impregnated activated carbon, drying at 120 deg.C for 8 hr, and then at 95 deg.C％Ar-5％H2And reducing and roasting for 3 hours at 600 ℃ in a mixed atmosphere to obtain the supported biomass liquefaction catalyst, wherein the carrier is activated carbon, the active center is Ni, the loading capacity is 10wt.%, the auxiliary agent is Co, the loading capacity is 2.5wt.%, and the loading capacity is 10% Ni-2.5% Co/AC.
The catalyst prepared in example 1 was used in examples 2 to 6.
Example 2
Pumping mixed slurry of wood chips, ethanol and 10% Fe/MgO (wherein the solid-liquid ratio of the wood chips to the ethanol is 1:8g/mL, and the content of the 10% Fe/MgO in the slurry is 8 wt.%) into an autoclave, introducing nitrogen to discharge air in the autoclave, not pressurizing, then heating to 340 ℃, immediately cooling the autoclave to room temperature by cold water after reaction is carried out for 30min, and taking out the materials for treatment. The yield of the liquid phase of the obtained product is 64.7 percent, the conversion rate of the raw material is 80.0 percent, and the heat value of the bio-oil is 33.04 MJ.kg-1。
Example 3
Pumping mixed slurry of enteromorpha, ethanol and 10% Fe/MgO (wherein the solid-liquid ratio of the enteromorpha to the ethanol is 1:8g/mL, and the content of the 10% Fe/MgO in the slurry is 8 wt.%) into an autoclave, introducing nitrogen to discharge air in the autoclave, not pressurizing, then heating to 340 ℃, immediately cooling the autoclave to room temperature by cold water after reaction for 30min, and taking out the materials for treatment. The yield of the liquid phase of the obtained product is 54.3 percent, the conversion rate of the raw material is 66.8 percent, and the heat value of the bio-oil is 27.38 MJ.kg-1。
Example 4
Pumping mixed slurry of wood chips, isopropanol and 10% Ni/AC (wherein the solid-to-liquid ratio of the wood chips to the isopropanol is 1:8g/mL, and the content of the 10% Ni/AC in the slurry is 8 wt.%) into an autoclave, introducing nitrogen to discharge air in the autoclave, not pressurizing, then heating to 340 ℃, immediately cooling the autoclave to room temperature by using cold water after reaction is kept for 30min, and taking out the materials for treatment. The yield of the liquid phase of the obtained product is 57.4 percent, the conversion rate of the raw material is 74.8 percent, and the heat value of the bio-oil is 30.44 MJ.kg-1。
Example 5
Mixing wood chips, ethanol and 10% Ni/AC mixed slurry (wherein the solid-to-liquid ratio of the wood chips to the ethanol is 1:8 g/m)L, the content of 10 percent Ni/AC in the slurry is 8 wt.%) is pumped into a high-pressure kettle, nitrogen is introduced to discharge air in the kettle, the pressure is not increased, then the temperature is increased to 340 ℃, the reaction is kept for 30min, the kettle is immediately cooled to room temperature by cold water, and the materials are taken out for treatment. The yield of the liquid phase of the obtained product is 60.7 percent, the conversion rate of the raw material is 74.3 percent, and the heat value of the bio-oil is 32.67 MJ.kg-1。
Example 6
The wood chips, ethanol and 10% Ni-2.5% Co/AC mixed slurry are pumped into a high-pressure kettle (wherein the solid-to-liquid ratio of the wood chips to the ethanol is 1:8g/mL, and the content of the 10% Ni-2.5% Co/AC in the slurry is 8 wt.%), nitrogen is introduced to discharge air in the kettle, the pressure is not increased, then the temperature is raised to 340 ℃, after reaction is kept for 30min, the kettle is immediately cooled to room temperature by cold water, and the materials are taken out for treatment. The yield of the liquid phase of the obtained product is 62.6 percent, the conversion rate of the raw material is 77.2 percent, and the heat value of the bio-oil is 32.83 MJ.kg-1。
Comparative example 1
Other conditions were the same as in example 2 except that 10% Fe/MgO was not added. The yield of the liquid phase of the obtained product is 57.0 percent, the conversion rate of the raw material is 70.2 percent, and the heat value of the bio-oil is 29.67 MJ.kg-1。
Comparative example 2
Other conditions were the same as in example 3 except that 10% Fe/MgO was not added. The yield of the liquid phase of the obtained product is 48.4 percent, the conversion rate of the raw material is 59.7 percent, and the heat value of the bio-oil is 25.38 MJ.kg-1。
The process conditions and yield data of examples 2 to 6 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 comparison of liquefaction results for examples 2-6 and comparative examples 1-2
Figure BDA0002077164210000101
As can be seen from table 1, in the case of omitting the catalyst (i.e., single hydrogen supply liquefaction), the conversion rate of the raw material, the liquid phase yield of the product, and the calorific value of the bio-oil are all reduced, which indicates that the supported biomass liquefaction catalyst of the present invention can catalyze the high-efficiency liquefaction conversion of the biomass, and the hydrogen supply-catalytic liquefaction coupling method provided by the present invention can fully utilize the synergistic effect to effectively promote the liquefaction conversion of the biomass.
According to the embodiments, the biomass hydrogen supply-catalytic liquefaction coupling method provided by the invention applies the supported biomass liquefaction catalyst to hydrogen supply liquefaction, fully utilizes the synergistic effect between the hydrogen supply agent and the catalyst, improves the conversion rate and the liquid phase yield of the biomass raw material, reduces the oxygen content of the liquid phase product, improves the heat value of the bio-oil, and overcomes the defects of high hydrogen consumption, low bio-oil yield and the like of the conventional single process; the catalyst provided by the invention has good catalytic liquefaction effect on biomass, and can be applied to a biomass hydrogen supply-catalytic liquefaction coupling process to realize efficient liquefaction and conversion of biomass.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A biomass hydrogen supply-catalytic liquefaction coupling method is characterized by comprising the following steps:
mixing biomass powder, a hydrogen donor solvent and a supported biomass liquefaction catalyst for liquefaction reaction to obtain a liquid-phase product; the supported biomass liquefaction catalyst comprises a carrier and an active center loaded on the carrier; the carrier is a porous material; the active center is Ni and/or Fe; the loading amount of the active center in the catalyst is 2-10 wt.%; the porous material is porous magnesium oxide; the preparation method of the porous magnesium oxide comprises the following steps: mixing the magnesium salt solution and the precipitant solution for aging, and drying and roasting the aged product in sequence to obtain porous magnesium oxide; the magnesium salt is Mg (CH)3COO)3·4H2O and/or MgCl2·6H2O; the precipitating agent is H2C2O4·4H2O，(NH4)2C2O4·H2One or more of O and anhydrous sodium carbonate; the aging temperature is 30-60 ℃, and the aging time is 6-12 h; the roasting temperature is 400-800 ℃, and the roasting time is 2-5 h; the specific surface area of the pores of the porous magnesium oxide is 86.54-203.51 m2(ii)/g, the average pore diameter is 5.68-26.58 nm; the hydrogen donor solvent is alcohol containing alpha-H; the liquefaction reaction is carried out in an inert atmosphere; pumping the mixed slurry into a high-pressure reaction kettle, purging the reaction kettle by using high-purity nitrogen to discharge air, stirring under the condition of no pressurization, and heating to the liquefaction reaction temperature.
2. The method of claim 1, wherein the raw material of the biomass powder is one or more of wood chips, algae, crop straw and nut shells;
the particle size of the biomass powder is 40-100 meshes.
3. The method according to claim 1, wherein the solid-to-liquid ratio of the biomass powder to the hydrogen donor solvent is 1: 2-10 g/mL; the mass content of the supported biomass liquefaction catalyst in the slurry obtained by mixing is 2-10%.
4. The method according to claim 1, wherein the temperature of the liquefaction reaction is 280 to 360 ℃ and the time is 20 to 60 min.
5. The method of claim 1, further comprising an auxiliary agent supported on a carrier; the auxiliary agent comprises one or more of Cu, Co, Mo and Ag; the loading amount of the auxiliary agent in the catalyst is 0.5-2.5 wt.%.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102051194A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Method for preparing liquid fuel from biomass through hydrogen-donor solvent
CN103242871A (en) * 2013-05-28 2013-08-14 中国石油大学(华东) Heavy oil and biomass hydrogenation coliquefaction treatment process
CN103265967A (en) * 2013-05-03 2013-08-28 浙江大学 Method for preparing bio-oil by liquefying biomass by high efficiency hydro-thermal method
CN104762099A (en) * 2015-03-19 2015-07-08 南京师范大学 Method for preparing light aromatic hydrocarbon compounds through solvent liquefaction coupled catalytic reforming of biomass
CN108285806A (en) * 2017-12-25 2018-07-17 北京三聚环保新材料股份有限公司 A kind of method of biomass direct liquefaction

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102051194A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Method for preparing liquid fuel from biomass through hydrogen-donor solvent
CN103265967A (en) * 2013-05-03 2013-08-28 浙江大学 Method for preparing bio-oil by liquefying biomass by high efficiency hydro-thermal method
CN103242871A (en) * 2013-05-28 2013-08-14 中国石油大学(华东) Heavy oil and biomass hydrogenation coliquefaction treatment process
CN104762099A (en) * 2015-03-19 2015-07-08 南京师范大学 Method for preparing light aromatic hydrocarbon compounds through solvent liquefaction coupled catalytic reforming of biomass
CN108285806A (en) * 2017-12-25 2018-07-17 北京三聚环保新材料股份有限公司 A kind of method of biomass direct liquefaction

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