WO2022166084A1 - Procédé de préparation et utilisation d'un catalyseur métallique de coordination de solvant - Google Patents

Procédé de préparation et utilisation d'un catalyseur métallique de coordination de solvant Download PDF

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Publication number
WO2022166084A1
WO2022166084A1 PCT/CN2021/103443 CN2021103443W WO2022166084A1 WO 2022166084 A1 WO2022166084 A1 WO 2022166084A1 CN 2021103443 W CN2021103443 W CN 2021103443W WO 2022166084 A1 WO2022166084 A1 WO 2022166084A1
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solvent
catalyst
metal catalyst
coordinated
preparing
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PCT/CN2021/103443
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English (en)
Chinese (zh)
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林鹿
陈高峰
曾宪海
孙勇
唐兴
雷廷宙
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厦门大学
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention belongs to the technical field of energy conversion and utilization, and in particular relates to a preparation method and application of a catalyst for preparing low-carbon alcohol from coal-based or biomass-based synthesis gas (CO+H 2 ).
  • CuCo-based catalysts are currently the most popular due to their abundant reserves, low price, mild reaction conditions, high CO hydrogenation activity and low-carbon alcohol selectivity, and strong carbon chain growth ability. Catalysts with industrial application prospects.
  • the bridge-adsorbed CO molecule dissociates and adsorbs on the Co 0 active site, the dissociated C * is directly hydrogenated to obtain CH y * , the CC is coupled and then hydrogenated to obtain C x H y * , and the Cu 0
  • the linear adsorption of CO occurs on the active site to generate non-dissociated CO *
  • C x H y * migrates to the Cu 0 active site and undergoes an insertion reaction with CO * to generate lower alcohols after hydrogenation.
  • the raw materials used are Cu(NO 3 ) 2 .3H 2 O, Co(NO 3 ) 2 .6H 2 O, Al(NO 3 ) 3 .9H 2 O, NaOH, Na 2 CO 3 and carbon nanotubes, and Commercially purchased expensive carbon nanotubes still need to be calcined at high temperature (350 °C) in the air for 2 hours to remove amorphous carbon, and then refluxed in a boiling solution of concentrated nitric acid and concentrated sulfuric acid at 100 °C for 4 hours, followed by deionized water. Finally, it was dried at 60° C. overnight to obtain the treated carbon nanotube carrier.
  • the CO conversion rate was 45.4% in the catalytic lower alcohol synthesis reaction, the yield of lower alcohol was 28.6%, and the catalyst stability was tested for 192 hours.
  • the catalyst system of the prior art has the defects of low CO conversion rate, poor catalyst stability, wide product carbon number distribution, especially poor ethanol selectivity, etc. It is necessary to further develop solvent formulations with high CO hydrogenation activity and low carbon alcohol selectivity. metal catalyst.
  • the purpose of the present invention is to overcome the deficiencies of the existing catalyst system, and cleverly design a solvent-coordinated metal catalyst with high CO hydrogenation activity and low carbon alcohol selectivity.
  • the invention provides a solvent-coordinated metal catalyst, which is characterized in that the catalyst uses a mesoporous material as a carrier, and is coordinated by a polyhydroxyl solvent and impregnated to reduce the active metal in situ, and the simultaneous confinement effect is in the pores of the mesoporous material.
  • the mesoporous material is selected from SBA-15, KIT-6 or MCM-41; the active metals are Cu and M, and M is selected from Co, Fe, Ni, Mn , Mo, or Nb, preferably Co; the polyhydroxy solvent ligand is selected from ethylene glycol, 1,2-propanediol, 1,4-butanediol, or glycerol.
  • the mesoporous material can be prepared by a known method or obtained by commercial purchase.
  • the weight percent composition of the catalyst is Cu: 1-30%, M: 1-30%, and the rest is a carrier, preferably, the weight percent composition of the catalyst is Cu: 7-13% , M: 7-13%, the rest are carriers.
  • the carrier has a specific surface area of 200-900 m 2 /g and an average pore size of 4-12 nm.
  • the present invention provides a method for preparing the above solvent-coordinated metal catalyst, which is characterized in that, using the mesoporous material as a carrier, a solvent-coordination impregnation method is used to confine the growth of Cu and M components in the pores of the mesoporous material, and after drying, The catalyst is obtained by pyrolysis in an inert atmosphere.
  • the confined growth of Cu and M nanoparticles in the pores is performed by using metal ions corresponding to Cu and M to coordinate with a polyhydroxy solvent, so that Cu and M are close to each other at the atomic level.
  • the immersion time is 12-24 h; the ratio of the metal ions corresponding to Cu and M is 3/1-1/3 (molar ratio).
  • the metal ions corresponding to Cu and M are in the form of nitrates.
  • the drying is vacuum drying at 100-150°C for 10-36h; the inert atmosphere is pyrolyzed under an inert atmosphere at 350-650°C for 2-8h; preferably, the inert atmosphere refers to N2 atmosphere.
  • the present invention also provides the application of the above-mentioned solvent-coordinated metal catalyst in the preparation of low-carbon alcohol from coal-based or biomass-based synthesis gas.
  • the present invention has the following characteristics: the selected polyhydroxy coordination type solvent ligands can coordinate Cu ions and M ions at the same time to form metal systems that are close to each other at the atomic level;
  • the amorphous carbon generated by the solution plays the role of in-situ reduction, eliminating the step of hydrogen reduction of metal oxides, simplifying the operation and saving energy;
  • the amorphous carbon plays the role of synchronously confining metal nanoparticles, inhibiting the degradation of metal particles. Agglomeration and sintering to obtain highly dispersed nanoscale active metal particles.
  • the catalyst carrier selected in the present invention adopts a mesoporous material with a high specific surface area (200-900 m 2 /g) and an average pore diameter of 4-12 nm, and the relatively large pores are favorable for the coordination growth of solvent-coordinated metals in the pores. .
  • the relatively large pores ensure high dispersion of active components and promote the diffusion of reactants and products in the pores, reducing mass transfer resistance.
  • the catalyst of the present invention has a good application in the preparation of low-carbon alcohols from coal-based/biomass-based synthesis gas. Compared with the prior art, it has the following advantages: the catalyst of the present invention can solve the problem of low CO conversion rate, poor stability, and wide product carbon number distribution in the process of preparing low-carbon alcohol from coal-based/biomass-based synthesis gas in the past. Especially the problem of poor ethanol selectivity.
  • the single-pass CO conversion rate of the catalyst of the present invention can be up to 82.4%; the water-gas shift activity on the catalyst is low, and the CO 2 selectivity is lower than 3%; the distribution of low-carbon alcohols in the product is narrow, and the selectivity of C1-C3 alcohols is good. up to 97%.
  • the catalyst of the invention has a controllable preparation process, good stability and low price, and has good industrial application prospects.
  • Figure 1 is an X-ray diffraction pattern (XRD) of the catalyst in the present invention.
  • Figure 2 is a transmission electron microscope (TEM) and particle statistics diagram of the catalyst in the present invention.
  • Fig. 3 is the XRD comparison diagram of the catalyst prepared by direct carbonization under the inert atmosphere in the present invention and the catalyst obtained by carbonization and air roasting and then hydrogen reduction.
  • Fig. 4 is the XRD comparison diagram of the catalyst prepared by using the solvent ligand 1,2 propylene glycol in the present invention and the catalyst obtained by deionized water as the solvent.
  • Fig. 5 is the stability evaluation result of the catalyst of Example 2 of the present invention.
  • Fig. 6 is the GC spectrum of the lower alcohol of the product obtained in Example 2 of the present invention.
  • Figure 7 is the MS spectrum of the product ethanol obtained in Example 2 of the present invention.
  • Figure 8 is the MS spectrum of the product n-propanol obtained in Example 2 of the present invention.
  • Figure 9 is the MS spectrum of the product n-butanol obtained in Example 2 of the present invention.
  • the weight percent composition of catalyst A is as follows: Cu 13%, Co 7%, and the balance is SBA-15.
  • the synthesis reaction of low-carbon alcohol is carried out in a high-pressure fixed-bed reactor.
  • analysis and sampling can be started after the catalyst runs for 24 hours.
  • the reaction raw materials, gas products and liquid products are analyzed on an Agilent GC 7890B. The results are shown in Table 1.
  • the weight percent composition of catalyst B is as follows: Cu 7%, Co 13%, and the balance is SBA-15.
  • the weight percent composition of catalyst C is as follows: Cu 10%, Co 10%, and the balance is SBA-15.
  • the synthesis reaction of low-carbon alcohol is carried out in a high-pressure fixed-bed reactor.
  • analysis and sampling can be started after the catalyst runs for 24 hours.
  • the reaction raw materials, gas products and liquid products are analyzed on an Agilent GC7890B. The results are shown in Table 1.
  • the weight percent composition of catalyst D is as follows: Cu 10%, Co 10%, and the balance is KIT-6.
  • the synthesis reaction of low-carbon alcohol is carried out in a high-pressure fixed-bed reactor.
  • analysis and sampling can be started after the catalyst runs for 24 hours.
  • the reaction raw materials, gas products and liquid products are analyzed on an Agilent GC7890B. The results are shown in Table 1.
  • the weight percent composition of catalyst E is as follows: Cu 8%, Co 12%, and the balance is KIT-6.
  • the synthesis reaction of low-carbon alcohol is carried out in a high-pressure fixed-bed reactor.
  • analysis and sampling can be started after the catalyst runs for 24 hours.
  • the reaction raw materials, gas products and liquid products are analyzed on an Agilent GC7890B. The results are shown in Table 1.
  • the catalysts of Examples 1-5 of the present invention were characterized by X-ray diffraction (XRD).
  • FIG. 2 shows the transmission electron microscope (TEM) and particle statistics of the catalyst prepared in the embodiment of the present invention.
  • the particle size calculated according to Scherrer's formula is about 5-6 nm, indicating that the CuCo nanoparticles are highly dispersed in the pores of the catalyst.
  • This excellent stability is due to the simultaneous coordination of CuCo ions by polyhydroxy solvent ligands, and the confined growth of nano-scale, high-dispersion active particles in the pores of the mesoporous material, and The amorphous carbon generated by the pyrolysis of solvent ligands also plays an effective role in inhibiting the agglomeration of copper nanoparticles, thereby improving the stability of the catalyst.
  • the source and properties of the carrier mesoporous silica SBA-15 are the same as those in Example 2.
  • the catalyst preparation steps of this comparative example are based on the preparation method steps in Example 2, and the following steps are further added: roasting in a muffle furnace at 400°C for 4 hours, and then reducing it in a hydrogen atmosphere at 450°C for 4 hours to obtain this comparative example.
  • the catalyst evaluation method is the same as that of Example 2, the catalyst evaluation results are shown in Table 3, and the XRD pattern thereof is shown in FIG. 3 .
  • the composition of the carrier is kept the same during the preparation process, and changing the decomposition and reduction process of the catalyst precursor has an important impact on the structure and activity of the final catalyst.
  • calcination under nitrogen atmosphere will pyrolyze the solvent ligands into amorphous carbon, which plays the role of in-situ reduction and fills the pores of the carrier as a dispersant to prevent the migration and agglomeration of active nanoparticles.
  • the confinement effect of carbon is lost by roasting in a muffle furnace, and the copper particles obtained under a hydrogen atmosphere are easy to agglomerate.
  • the catalyst obtained by direct inert atmosphere pyrolysis of the present invention has higher CO conversion rate and lower alcohol selectivity.
  • the source and properties of the carrier mesoporous silica SBA-15 are the same as those in Example 2.
  • the catalyst preparation steps of this comparative example refer to the preparation method in Example 2, and the only difference is that deionized water is used as the solvent, namely 1.0 g of copper nitrate (Cu(NO 3 ) 2 ⁇ 3H 2 O), 2.6 g of cobalt nitrate (Co(NO 3 ) 2 ⁇ 6H 2 O) was dissolved in 20 mL of deionized water, and the subsequent steps were the same as those in Example 2 to obtain the catalyst of this comparative example.
  • the catalyst evaluation method is the same as that in Example 2, and the catalyst evaluation results are shown in Table 4.
  • the source and properties of the carrier mesoporous silica SBA-15 are the same as those in Example 2.
  • the preparation steps of the catalyst of this comparative example are basically the same as those of the preparation method in Example 2, except that the last step is calcination at 400° C. for 5 h under N 2 atmosphere to obtain the catalyst of this comparative example.
  • the catalyst evaluation method is the same as that in Example 2, and the catalyst evaluation results are shown in Table 5.
  • the in-situ carbonization of the solvent ligands of the catalyst precursor at 550 °C can achieve higher CO conversion and higher selection of low-carbon alcohols than at 400 °C, and the distribution of alcohol products to low-carbon Alcohol orientation shift. Therefore, in the present invention, the catalyst obtained by carbonizing and decomposing the catalyst precursor at 550° C. is used in the low-carbon alcohol synthesis system.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention appartient au domaine technique de la conversion et de l'utilisation d'énergie et concerne en particulier un procédé de préparation et l'utilisation d'un catalyseur pour préparer un alcool inférieur à partir d'un gaz de synthèse (CO + H2) de charbon/biomasse, etc. Le catalyseur utilise un matériau mésoporeux comme support. Des ions métalliques sont induits pour entrer dans l'intérieur d'un canal de pore du support au moyen d'une coordination entre un ligand de solvant polyhydroxy et les ions métalliques et les ions métalliques sont proches l'un de l'autre sur l'échelle atomique. Dans une atmosphère inerte à haute température, le carbone amorphe généré par pyrolyse du ligand de solvant peut réduire un métal dans un état de valence élevé en nanoparticules actives in situ. Les canaux de pore du matériau mésoporeux et le carbone amorphe exercent conjointement un effet de confinement synchrone, de manière à inhiber efficacement l'agglomération et le frittage de particules métalliques et à obtenir des particules métalliques actives à l'échelle nanométrique, à activité élevée et à dispersion élevée. L'utilisation du catalyseur de la présente invention peut résoudre les problèmes antérieurs d'un faible taux de conversion de CO, d'une mauvaise stabilité du catalyseur, d'une large distribution du nombre d'atomes de carbone dans le produit et, en particulier, une faible sélectivité pour l'éthanol, pendant le procédé de préparation d'un alcool inférieur à partir de gaz de synthèse à base de charbon ou à base de biomasse.
PCT/CN2021/103443 2021-02-04 2021-06-30 Procédé de préparation et utilisation d'un catalyseur métallique de coordination de solvant WO2022166084A1 (fr)

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CN112844446B (zh) * 2021-02-04 2022-06-28 厦门大学 一种溶剂配位金属催化剂的制备方法及应用
CN113522339B (zh) * 2021-07-20 2022-08-30 厦门大学 一种加氢m@c-n催化剂的制备方法及应用
CN115254114B (zh) * 2022-08-01 2024-05-14 厦门大学 一种生物质基M@Biomass-C催化剂的制备方法及应用

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