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Loading type composite metal-acid bifunctional catalyst

A bifunctional catalyst, composite metal technology, applied in molecular sieve catalysts, catalyst activation/preparation, physical/chemical process catalysts, etc., can solve problems such as catalyst deactivation, achieve simple preparation process, simple reaction process, excellent activity and orientation selective effect

Inactive Publication Date: 2018-06-22
昆山普瑞凯纳米技术有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in the cycle test of the catalyst, the catalyst showed obvious deactivation in the third cycle reaction

Method used

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  • Loading type composite metal-acid bifunctional catalyst
  • Loading type composite metal-acid bifunctional catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Catalyst preparation

[0022] Preparation of one or more modified carriers among lanthanum, cerium, praseodymium and neodymium: Weigh 1g of activated carbon, alumina, titanium dioxide, Y-type molecular sieve, ZSM-5, β-molecular sieve and other carriers, and add them to NH4Cl Mix and stir in the solution evenly, then add LaCl3, CeCl3, PrCl3, NdCl3 aqueous solutions with 5wt% equivalents of rare earth elements respectively, and keep the obtained mixed solution in a water bath at 80°C for 1 hour, filter, wash, and then calcined at 600°C After 2 hours, the preparation of a carrier modified by one or more of lanthanum, cerium, praseodymium and neodymium (active component B) was obtained.

[0023] Preparation of supported metal-acid bifunctional catalyst (active component A+B):

[0024] Experiment 1: Preparation of metal catalyst 2wt% Ru / H-Y: Weigh 0.1250 g of hexaammine ruthenium chloride in a clean 50 ml round bottom flask, add 25 ml of ultrapure water, place the round bot...

Embodiment 2

[0031] Controlled experiment

[0032] Experiment 4: The catalyst similar to Example 1 is used for the preparation of composite catalyst Ru / C+La-Y: take 5wt% Ru / C 0.1g respectively, La-Y molecular sieve 0.4g, obtain composite catalyst through mechanical mixing Ru / C+La-Y. Under the same experimental conditions, although the non-supported catalyst Ru / C+La-Y can realize the complete conversion of levulinic acid ester, the selectivity of valeric acid (ester) is not high, only 2%.

[0033] Experiment 5-7: The preparation method is the same as in Example 1, and 2wt% Pt / La-Y, 2wt% Ru / H-ZSM5 and 2wt% Pt / H-ZSM5 are prepared. Under the condition of adding solvent, the selectivity of valeric acid (ester) is not high.

[0034] Catalyst activity test: add 5g of ethyl levulinate or 2g of ethyl levulinate with 18g of solvent, 0.5g of catalyst into a 50ml reaction kettle, replace the gas with nitrogen for three times, then replace with hydrogen for three times, and then fill with hydrogen t...

Embodiment 3

[0036] The conversion effect of the 2wt%Ru / La-Y catalyst for the selective hydrogenation of ethyl levulinate in five cycles of experiments is shown in Table 2:

[0037] Catalyst cycle test: Add 5g of ethyl levulinate and 0.5g of catalyst into a 50ml reactor, pass through nitrogen to replace the gas three times, then pass through hydrogen to replace three times, then fill with hydrogen to 4MPa, heat up to 220°C and stir for 10h. After the reaction, the catalyst was filtered, recovered, washed three times with ethanol, air-dried, and then put into the next cycle reaction.

[0038] Table 2 1wt%Ru / La-Y Catalyst Cycle Experiment Results

[0039]

[0040] The 2wt% Ru / La-Y catalyst still achieves complete conversion to ethyl levulinate after five cycles of experiments, and the total yield of valeric acid and valeric acid esters remains above 90%. This catalyst has excellent stability.

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Abstract

The invention discloses a loading type composite metal-acid bifunctional catalyst. The loading type composite metal-acid bifunctional catalyst is prepared from a catalytic activity component, a carrier and an rare earth element; the catalytic activity component is one or more of transition metal iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, platinum and gold; the carrier isone or more of active carbon, aluminum oxide, titanium dioxide, Y-shaped molecular sieve, ZSM-5 and beta-molecular sieve; and the rare earth element is one or more of oxides of lanthanum, cerium, praseodymium and neodymium. According to a method for preparing valeric acid (valerate) by adopting the loading type composite metal-acid bifunctional catalyst, levulinic acid platform molecules are takenas a reaction raw material to be subjected to a hydrogenation reaction in a sealed high pressure reaction still, wherein the reaction temperature is 50-400 DEG C, the hydrogen pressure is 1-20 MPa, and the reaction time is no less than 60 minutes. The composite metal-acid bifunctional catalyst disclosed by the invention presents the high activity, the high selectivity and the excellent stabilityunder a hydrothermal condition.

Description

technical field [0001] The invention relates to a catalyst, in particular to a supported composite metal-acid bifunctional catalyst. Background technique [0002] Supported composite metal-acid bifunctional catalysts have a wide range of industrial applications, such as hydrogenation, dehydrogenation, isomerization, and cracking reactions. How to effectively construct a complex active site structure with a fine structure is the key technology for preparation. [0003] Biomass resources, as an important renewable resource, compared to other different types of renewable resources, such as wind energy, water energy, nuclear energy, solar energy, etc., it is the only fuel and chemical It is a carbon source for products and has great potential to replace traditional fossil energy alternatives. Among them, the levulinic acid platform molecule is considered to be one of the very promising and important biomass platform molecules. Levulinic acid can be further converted into a va...

Claims

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Application Information

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IPC IPC(8): B01J29/44B01J29/46B01J29/12B01J29/14B01J37/10B01J37/08C07C51/377C07C53/126C07C67/317C07C69/24
CPCB01J29/126B01J29/146B01J29/44B01J29/46B01J37/082B01J37/10B01J2229/18C07C51/377C07C67/317C07C53/126C07C69/24
Inventor 罗文豪谢林峰
Owner 昆山普瑞凯纳米技术有限公司
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