CN113262796B - Non-noble metal catalyst and method for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthetic gas by using same - Google Patents
Non-noble metal catalyst and method for producing low-carbon alcohol liquid fuel by catalytically reforming biomass synthetic gas by using same Download PDFInfo
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- 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
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- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
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Abstract
The invention relates to a non-noble metal catalyst, which is prepared by loading a metal component I and a metal component 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 a mixture of more than two of lithium, sodium, potassium and cesium in any proportion. Catalytic reforming of biomass synthesis gas using the non-noble metal catalyst to produce low carbon alcohol liquid fuel, methanol (CH) in the low carbon alcohol based fuel 3 OH), ethanol (C) 2 H 5 OH) content is high.
Description
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 using the same to catalyze and reform biomass synthesis gas.
Background
With the exhaustion of fossil energy and the serious environmental problems such as haze caused by the use of fossil energy, people are increasingly researching alternative fossil energy. Meanwhile, in recent years, the atmospheric pollution caused by straw burning seriously affects the clothes and food residence of people, endangers the health of human beings, and the wish of straw conversion and utilization is stronger. On the other hand, biomass energy contained in the straw has the characteristics of rich resources, high combustion heat value and wide application range, so that the biomass energy 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 is used for realizing the breakthrough of the technology for synthesizing the mixed alcohol fuel by gasifying the low-quality biomass 2 High content, complex reaction in the synthesis process of low-carbon alcohol, and more byproducts, and develops CO resistance 2 The green chemical synthesis and the precise separation process of the high-efficiency and high-selectivity chemical catalyst and the low-carbon alcohol are key to 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 using the same to catalyze and reform biomass synthetic gas, wherein in the low-carbon alcohol-based fuel prepared by the method, methanol (CH) 3 OH), ethanol (C) 2 H 5 OH) content is high.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a non-noble metal catalyst is prepared from metal component A and metal component B through immersing to load on cordierite, the first metal component is copper, molybdenum or manganese (such as Cu 2+ 、Mo 4+ 、Mo 6+ 、Mn 2+ 、Mn 4+ Etc.), one or a mixture of two or more of them in any proportion; the second metal component is one or a mixture of more than two of alkali metal lithium, sodium, potassium, sodium and the like in any proportion.
Further, the first metal component accounts for 1-3% of the weight of the catalyst, and the second metal component 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) A soluble salt solution of the metal component one (e.g. Cu (NO) 3 ) 2 、Mn(NO 3 ) 2 、Mn(NO 3 ) 4 、Mo(NO 3 ) 4 、MoO 4 (NH 4 ) 2 Or MoO 3 (NH 4 ) 2 Etc.), adding chloride of the second metal component (such as LiCl, naCl, KCl, csCl etc.), stirring for dissolving, then adding carrier cordierite, and vacuum impregnating for 20-28h;
2) Transferring into an oven, drying at 110-130deg.C for 4-6h, and calcining at 600-700deg.C for 5-7h;
3) Grinding the calcined product of the step 2) into powder, pressing and cutting into particles with 20-40 meshes to obtain the composite material.
Further preferably, the carrier cordierite in the step 1) is boiled with 30% oxalic acid solution for 30min in advance to expand the volume, then washed with distilled water to be neutral, dried and ground for later use.
The invention also provides a method for producing the low-carbon alcohol liquid fuel by catalyzing and reforming the biomass synthesis gas by using the non-noble metal catalyst, which comprises the following steps: the biomass synthesis gas after reforming and purifying is used for producing low-carbon alcohol liquid fuel under the condition of existence of a non-noble metal catalyst and at the reaction pressure of 3-5Mpa and the reaction temperature of 200-350 ℃.
The original biomass synthesis gas component is not suitable for directly synthesizing low-carbon alcohol, and after the original biomass synthesis gas is reformed and purified in the early stage, the basic components of the biomass synthesis gas are adjusted as shown in table 1, and mainly H is used 2 The 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 invention relates to a method for preparing reformed and purified biomass synthesis gas, which comprises the following steps of:
at present, catalysts for preparing alcohol-based liquid fuel by gasifying fuel gas through biomass are 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 the industrial requirement is still not met, and the catalyst is mainly characterized 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, because the reaction is often accompanied by side reactions such as water gas conversion, hydrocarbons and the like, a series of problems such as low selectivity of low-carbon alcohol in the product, wide carbon number distribution of the alcohol product and the like are caused, and the large-scale application of the Cu-Co-based catalyst is severely restricted, the modification and modification of the Cu-Co-based catalyst are hot spots and difficulties of the current research, and the main focus is on the selection of catalyst auxiliaries, the selection of carriers, the change of the content of supported active components and the change of the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst is prepared by compounding the first metal component and the second alkali metal component, wherein the first metal component and the second alkali metal component form a synergistic effect, and different metal atoms form metal compounds with different forms on the surface of the catalyst, so that the active sites on the surface of the catalyst are enhanced, and the catalytic effect is improved. The second alkali metal component has the purpose of adjusting the strong and weak acid acidity and the acid quantity of the catalyst surface, and mainly adjusts the surface structure and the acid-base property of the catalyst surface. The synergistic effect between the components of the first metal component is a key for improving the selectivity of the low-carbon alcohol, and the way for realizing the synergistic effect is to form a state that the metal components (such as Cu, mo, cu, mn and the like) are closely contacted in the catalyst, so that the catalyst is more suitable for preparing the low-carbon alcohol-based liquid fuel by adopting biomass synthesis gas, and has better practical application significance for promoting biomass energy utilization, conversion and popularization of new energy sources to realize carbon neutralization.
Detailed Description
The following describes the technical scheme of the present invention in further detail with reference to examples, but the scope of the present invention is not limited thereto.
In the embodiment of the invention, the raw materials such as cordierite and the like are all common commercial products.
Example 1
The non-noble metal catalyst is prepared by loading a metal component I and a metal component I on a carrier cordierite through an impregnation method, wherein the metal component I is a mixture composed of copper and molybdenum; the second metal component is alkali metal lithium; the copper and the molybdenum account for 1% of the weight of the catalyst, and the alkali metal lithium accounts for 1% of the weight of the catalyst.
The preparation method of the non-noble metal catalyst comprises the following steps:
1) 150g of carrier cordierite is boiled for 30min in advance by 30% oxalic acid solution, then is washed to be neutral by distilled water, and is dried and ground for standby;
2) 2.951g Cu (NO) was weighed out 3 ) 2 、2.042gMoO 4 (NH 4 ) 2 Dissolving with 100ml distilled water to prepare a solution; adding 1.912g of KCl, stirring and dissolving, then adding 100g of the carrier cordierite treated in the step 1), and soaking for 24 hours at the room temperature of 20-25 ℃ in vacuum (0.06 Mpa);
3) Transferring into an oven, drying at 120 ℃ for 5 hours, and calcining at 650 ℃ for 6 hours in a muffle furnace;
4) Grinding the calcined product of step 3) into powder, pressing on a tablet press by conventional technique, and cutting into 20-40 mesh granules to obtain catalyst 1% Cu 2+ -1%Mo 6+ -1% k/cordierite.
Examples 2 to 9
With reference to the procedure of example 1, the corresponding catalysts were prepared by replacing the soluble salts of metal component one and the chlorides of metal component two in different classes, as detailed in Table 1 below.
Catalytic test
The method for producing the low-carbon alcohol liquid fuel by catalyzing and reforming the biomass synthesis gas by using the non-noble metal catalyst prepared in the above examples 1 to 9 specifically comprises the following steps: the reformed and purified biomass synthesis gas is used for producing low-carbon alcohol liquid fuel under the condition of existence of non-noble metal catalyst at a certain reaction pressure and reaction temperature, and the result is shown in table 1 (C 3+ OH refers to alkyl alcohols of three or more carbons). The main gas component in the reformed and purified biomass synthesis gasThe volume percentages are referred to as follows:
the phase change exists when the gas is converted into the liquid, the requirements on the reaction temperature and the pressure are high, and the catalyst is introduced to reduce the harsh reaction conditions, so that the reaction temperature and the reaction pressure are reduced, and the cost is reduced. 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 the test screening, the introduction of non-noble metals such as Cu, mo, mn and the like has better catalytic reaction effect, and methanol (CH) 3 OH), ethanol (C) 2 H 5 OH) content was high and the test performance is shown in Table 1. Table 1 shows the performance results of the catalysts prepared in examples 1 to 9 after reacting for 4 hours at a certain temperature and pressure for producing low-carbon alcohol liquid fuel by catalytic reforming biomass synthesis gas, and specifically shows methanol MeOH, ethanol EtOH and tri-carbon alcohol and C above 3+ Percentage selectivity of OH liquid fuel. The pure supported alkali metal component II has no catalytic effect; the pure supported metal component resulted in a product with greater gas selectivity and less liquid alcohol product, not provided in table 1.
Table 1 performance results of catalysts of examples 1 to 9 for catalytic reforming of biomass syngas to produce lower alcohol liquid fuels
Finally, it should be noted that the above list is only specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but 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 (4)
1. The application of a non-noble metal catalyst in the production of low-carbon alcohol liquid fuel by catalytic reforming of biomass synthesis gas 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 a mixture of more than two of copper, molybdenum or manganese in any proportion; the second metal component is one or a mixture of more than two of lithium, sodium, potassium and cesium in any proportion;
the first metal component accounts for 1-3% of the weight of the catalyst, and the second metal component accounts for 0.5-2% of the weight of the catalyst.
2. The use according to claim 1, wherein the non-noble metal catalyst is prepared by:
1) Weighing and preparing a soluble salt solution of a first metal component according to a proportion, adding a chloride of a second metal component, stirring for dissolution, adding a carrier cordierite, and carrying out vacuum impregnation for 20-28h;
2) Transferring into an oven, drying at 110-130deg.C for 4-6h, and calcining at 600-700deg.C for 5-7h;
3) Grinding the calcined product of the step 2) into powder, pressing and cutting into particles with 20-40 meshes to obtain the composite material.
3. The use according to claim 2, wherein the carrier cordierite in step 1) is boiled in advance with 30% oxalic acid solution for 30min, then rinsed with distilled water to neutrality, dried and ground for use.
4. The use according to claim 1, wherein the reformed and purified biomass synthesis gas is used for producing low-carbon alcohol liquid fuel in the presence of a non-noble metal catalyst at a reaction pressure of 3-5Mpa and a reaction temperature of 200-350 ℃.
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| US5070058A (en) * | 1990-01-22 | 1991-12-03 | Texaco, Inc. | Method for making a catalyst composition used in the production of lower aliphatic alcohols |
| US9636665B2 (en) * | 2010-12-06 | 2017-05-02 | Georgia Tech Research Corporation | Catalyst compositions for converting syngas to produce higher alcohols |
| CN104148078B (en) * | 2014-07-17 | 2016-10-19 | 中国科学院广州能源研究所 | A kind of for biomass synthesis gas catalyst producing low-carbon alcohols and preparation method thereof |
| CN105833842A (en) * | 2015-01-13 | 2016-08-10 | 江苏瑞丰科技实业有限公司 | Granular non-noble-metal efficient integrated air purification composite material |
| CN105670710B (en) * | 2016-02-02 | 2018-05-08 | 河南省科学院能源研究所有限公司 | A kind of method using hydrogen peroxide as raw material reforming biomass crude synthesis gas |
| CN107376937B (en) * | 2017-08-14 | 2018-08-28 | 河南省科学院能源研究所有限公司 | A kind of order mesoporous composite catalyst and its preparation method and application |
| CN107737524B (en) * | 2017-10-24 | 2021-06-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Air purification module for removing formaldehyde in indoor air pollutants and preparation method and application thereof |
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| CoCu-K/ZrO_2-Al_2O_3催化剂的制备及其在合成气制备低碳醇中的应用;陈高峰;雷廷宙;徐海燕;杨延涛;朱金陵;何晓峰;;河南科学(10);第93-97页 * |
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