CN113262796A - Non-noble metal catalyst and method for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthesis gas with same - Google Patents

Non-noble metal catalyst and method for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthesis gas with same Download PDF

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CN113262796A
CN113262796A CN202110629911.0A CN202110629911A CN113262796A CN 113262796 A CN113262796 A CN 113262796A CN 202110629911 A CN202110629911 A CN 202110629911A CN 113262796 A CN113262796 A CN 113262796A
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catalyst
metal component
noble metal
metal catalyst
carbon alcohol
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CN113262796B (en
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杨延涛
杨树华
关倩
徐海燕
徐亚丹
李在峰
何晓峰
张竟月
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Henan Academy of Sciences
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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
    • B01J23/76—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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
    • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst

Abstract

The invention relates to a non-noble metal catalyst, which is prepared by loading a metal component I and a metal component II on a carrier cordierite through an impregnation method, wherein the metal component I is one or a mixture of more than two of copper, molybdenum or manganese in any proportion; the second metal component is one or the mixture of more than two of lithium, sodium, potassium and cesium in any proportion. The non-noble metal catalyst is used for catalyzing and reforming biomass synthesisGas generation for producing low carbon alcohol liquid fuel, methanol (CH) in low carbon alcohol base fuel3OH), ethanol (C)2H5OH) content is higher.

Description

Non-noble metal catalyst and method for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthesis gas with same
Technical Field
The invention belongs to the technical field of biomass energy synthesis, and particularly relates to a non-noble metal catalyst and a method for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthesis gas by using the non-noble metal catalyst.
Background
With the gradual depletion of fossil energy and the more serious environmental problems such as haze caused by the use of fossil energy, people have more and more researches on alternative energy of fossil energy. Meanwhile, in recent years, with air pollution caused by straw burning, clothes and eating habits of people are seriously influenced, the health of human is more harmed, and people have stronger and stronger desire for straw conversion and utilization. On the other hand, the biomass energy contained in the straw has the characteristics of rich resources, high combustion heat value and wide application range, so that the straw is an ideal new energy source.
The low-quality biomass has the characteristics of low cellulose, high water content, high ash content and the like, so that the gasification efficiency is low, the purification is difficult, the hydrogen-carbon ratio of the synthesis gas is not high, and the CO in the biomass-based synthesis gas breaks through the technology for synthesizing the mixed alcohol fuel by gasifying the low-quality biomass2High content, complex reaction and more byproducts in the synthesis process of the low carbon alcohol, and development of CO resistance2The efficient and high-selectivity chemical catalyst and the green chemical synthesis and accurate separation process of the low-carbon alcohol are key points for improving the yield and the selectivity of the low-carbon alcohol.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a non-noble metal catalyst and a method for producing low-carbon alcohol liquid fuel by utilizing the non-noble metal catalyst to catalytically reform biomass synthesis gas, wherein methanol (CH) in the low-carbon alcohol-based fuel prepared by the method3OH), ethanol (C)2H5OH) content is higher.
In order to achieve the purpose, the invention adopts the following technical scheme:
a non-noble metal catalyst is prepared from the first metal component (Cu, Mo or Mn) and the metal component (Cu, etc) through loading them on cordierite carrier by immersion method2+、Mo4+、Mo6+、Mn2+、Mn4+Etc.) in any ratio; the second metal component is one or mixture of more than two of alkali metal lithium, sodium, potassium, cesium and the like in any proportion.
Further, the metal component I accounts for 1-3% of the weight of the catalyst, and the metal component II accounts for 0.5-2% of the weight of the catalyst.
The invention provides a preparation method of the non-noble metal catalyst, which comprises the following steps:
1) weighing and preparing soluble salt solution of metal component I (such as Cu (NO)3)2、Mn(NO3)2、Mn(NO3)4、Mo(NO3)4、MoO4(NH4)2Or MoO3(NH4)2Etc.), adding chloride of the second metal component (such as LiCl, NaCl, KCl, CsCl, etc.), stirring for dissolving, then adding carrier cordierite, and carrying out vacuum impregnation for 20-28 h;
2) drying in a drying oven at the temperature of 110-130 ℃ for 4-6h, and then calcining at the temperature of 600-700 ℃ for 5-7 h;
3) grinding the calcined product obtained in the step 2) into powder, pressing and cutting the powder into particles of 20-40 meshes to obtain the catalyst.
Further preferably, the carrier cordierite obtained in step 1) is boiled with 30% oxalic acid solution for 30min in advance for expansion, and then is washed with distilled water to be neutral, dried and ground for later use.
The invention also provides a method for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthesis gas by using the non-noble metal catalyst, which comprises the following steps: the reformed and purified biomass synthesis gas is used for producing the low-carbon alcohol liquid fuel under the conditions of 3-5Mpa of reaction pressure and 200-350 ℃ of reaction temperature in the presence of a non-noble metal catalyst.
The components of the original biomass synthesis gas are not suitable for directly synthesizing low-carbon alcohol, and the basic components of the biomass synthesis gas are adjusted as shown in table 1 after the original biomass synthesis gas is reformed and purified in the early stage, and most importantly, H is used2The ratio of the/CO is adjusted to be about 2, and the method is more suitable for directly synthesizing the low-carbon alcohol liquid fuel in the next step. The volume percentage of main gas components in the reformed and purified biomass synthesis gas is referred to as follows:
Figure DEST_PATH_IMAGE001
。
at present, the internationally developed catalysts for preparing alcohol-based liquid fuel by biomass gasification gas comprise noble metal catalysts, molybdenum-based catalysts, modified methanol catalysts, modified Fischer-Tropsch synthesis catalysts and the like. In recent years, the reaction performance of the newly developed synthetic alcohol-based liquid fuel catalyst is greatly improved in activity and selectivity, but still cannot meet the industrial demand, mainly manifested by poor CO hydrogenation activity and low CO conversion rate; the reaction temperature is higher, and the reaction is generally carried out at 300-400 ℃. However, the reaction is accompanied by the occurrence of water gas conversion, hydrocarbons and other side reactions, which leads to a series of problems of low selectivity of low carbon alcohol in the product, wide carbon number distribution of the alcohol product and the like, and severely restricts the large-scale application of the Cu-Co-based catalyst, so that modification of the Cu-Co-based catalyst is a hotspot and a difficulty of current research, and mainly focuses on the selection of catalyst auxiliaries, the selection of carriers, the change of the content of loaded active components and the change of a preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst is prepared by compounding the metal component I and the alkali metal component II, wherein the components of the metal component I form a synergistic effect, different metal atoms form metal compounds with different forms on the surface of the catalyst, and the active point positions on the surface of the catalyst are enhanced, so that the catalytic effect is improved. The alkali metal component II plays a role in adjusting the strong and weak acidity and the acidity amount of the surface of the catalyst, and mainly adjusts the surface structure and the acidity and alkalinity of the surface of the catalyst. The synergistic effect among the components of the first metal component is the key for improving the selectivity of the low-carbon alcohol, and the way for realizing the synergistic effect is to form the state of close contact of the metal components (such as Cu, Mo, Cu, Mn and the like) in the catalyst, so that the method is more suitable for preparing the low-carbon alcohol-based liquid fuel by adopting the biomass synthesis gas, and has better practical application significance for promoting the utilization and conversion of biomass energy and popularizing new energy to realize carbon neutralization.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the examples of the present invention, the raw materials such as cordierite and the like are all common commercially available products.
Example 1
A non-noble metal catalyst is prepared by loading a metal component I and a metal component II on a carrier cordierite through an impregnation method, wherein the metal component I is a mixture of copper and molybdenum; the metal component II is alkali metal lithium; the copper and the molybdenum both account for 1 percent of the weight of the catalyst, and the alkali metal lithium accounts for 1 percent of the weight of the catalyst.
The preparation method of the non-noble metal catalyst comprises the following steps:
1) boiling 150g of carrier cordierite with 30% oxalic acid solution for 30min in advance, then washing the carrier cordierite with distilled water to be neutral, and drying and grinding the carrier cordierite for later use;
2) weighing 2.951g Cu (NO)3)2、2.042gMoO4(NH4)2Dissolving with 100ml distilled water to prepare solution; adding 1.912g of KCl, stirring for dissolving, then adding 100g of the carrier cordierite treated in the step 1), and soaking for 24 hours at room temperature of 20-25 ℃ in vacuum (0.06 Mpa);
3) drying in a drying oven at 120 deg.C for 5h, and calcining in a muffle furnace at 650 deg.C for 6 h;
4) grinding the calcined product obtained in the step 3) into powder, pressing and cutting the powder into particles of 20-40 meshes on a tablet press by adopting the conventional technology, and obtaining the catalyst which is recorded as 1% Cu2+-1%Mo6+1% K/cordierite.
Examples 2 to 9
Corresponding catalysts were prepared by replacing the soluble salts of the first metal component and the chlorides of the second metal component of different kinds according to the method of example 1, as detailed in table 1 below.
Catalytic test
The method for producing the low-carbon alcohol liquid fuel by catalytically reforming the biomass synthesis gas by using the non-noble metal catalyst prepared in the above embodiments 1 to 9 specifically comprises the following steps: the reformed and purified biomass synthesis gas is used for producing the low-carbon alcohol liquid fuel under certain reaction pressure and reaction temperature in the presence of a non-noble metal catalyst, and the result is shown in the table 1 (C)3+OH refers to alkyl alcohols having three or more carbons). The volume percentage of main gas components in the reformed and purified biomass synthesis gas is referred to as follows:
Figure DEST_PATH_IMAGE002
。
the phase change of gas to liquid exists, the requirements on reaction temperature and pressure are high, and the purpose of introducing the catalyst is to reduce harsh reaction conditions, reduce the reaction temperature and the reaction pressure and reduce the cost. The noble metal catalyst has excellent reaction performance, but the cost is too high to be suitable for large-scale development and utilization, and the non-noble metal catalyst is adopted, so that the catalyst cost is saved while the catalytic effect is not obviously reduced, the production cost is reduced, and the large-scale production and use are facilitated. From experimental screening, the introduction of non-noble metals such as Cu, Mo and Mn has better catalytic reaction effect, and methanol (CH)3OH), ethanol (C)2H5OH) content was higher and the test properties are detailed in Table 1. Table 1 shows the performance results of the catalysts prepared in examples 1 to 9 for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthesis gas after reacting for 4 hours at certain temperature and pressure, and specifically shows methanol MeOH, ethanol EtOH, and three-carbon alcohol and C above3+Percent selectivity of OH liquid fuel. The pure supported alkali metal component II has no catalytic effect; purely supported metal groupWhile, the product was more gas selective and less liquid alcohol product, not provided in table 1.
Table 1 examples 1 to 9 performance results of catalytic reforming of biomass syngas to produce lower alcohol liquid fuels
Figure DEST_PATH_IMAGE003
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (5)

1. A non-noble metal catalyst is characterized in that the catalyst is prepared by loading a metal component I and a metal component II on a carrier cordierite through an impregnation method, wherein the metal component I is one or a mixture of more than two of copper, molybdenum or manganese in any proportion; the second metal component is one or the mixture of more than two of lithium, sodium, potassium and cesium in any proportion.
2. A non-noble metal catalyst as claimed in claim 1, wherein the first metal component comprises from 1 to 3% by weight of the catalyst and the second metal component comprises from 0.5 to 2% by weight of the catalyst.
3. A process for the preparation of a non-noble metal catalyst as claimed in claim 1 or 2, characterized in that it comprises the following steps:
1) weighing and preparing soluble salt solution of the first metal component according to the proportion, adding chloride of the second metal component, stirring for dissolving, then adding carrier cordierite, and carrying out vacuum impregnation for 20-28 h;
2) drying in a drying oven at the temperature of 110-130 ℃ for 4-6h, and then calcining at the temperature of 600-700 ℃ for 5-7 h;
3) grinding the calcined product obtained in the step 2) into powder, pressing and cutting the powder into particles of 20-40 meshes to obtain the catalyst.
4. The method for preparing a non-noble metal catalyst according to claim 3, wherein the cordierite as the carrier in step 1) is boiled in a 30% oxalic acid solution for 30min, then washed to be neutral by distilled water, dried and ground for later use.
5. The method for producing the low-carbon alcohol liquid fuel by catalytically reforming the biomass synthesis gas by using the non-noble metal catalyst as claimed in claim 1 or 2, wherein the reformed and purified biomass synthesis gas is used for producing the low-carbon alcohol liquid fuel under the conditions of the presence of the non-noble metal catalyst and under the reaction pressure of 3-5Mpa and the reaction temperature of 200-350 ℃.
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