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Selective hydrogenation method for methanol to olefin product

A technology for producing olefins from methanol and selective hydrogenation, which is applied to the selective hydrogenation of propyne and propadiene, and the field of iron-based hydrogenation catalysts for trace acetylene. , low conversion rate of acetylene, etc., to achieve the effects of excellent anti-coking performance, moderate reactivity and low ethylene loss rate

Inactive Publication Date: 2018-07-06
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This technology is to prepare intermetallic compounds under high temperature conditions for selective hydrogenation of acetylene. The conversion rate of acetylene is low and the reaction temperature is high, which is not conducive to industrial application.
And the catalyst is prepared by hot melting method, the conditions are harsh
[0035] To sum up, the selective hydrogenation of low-carbon alkynes and dienes currently mainly uses noble metal catalysts, and a lot of work has been done on the research and development of non-noble metal catalysts, but there is still a long way to go before industrial applications

Method used

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  • Selective hydrogenation method for methanol to olefin product
  • Selective hydrogenation method for methanol to olefin product
  • Selective hydrogenation method for methanol to olefin product

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0099] Weigh a clover-shaped alumina carrier of Φ4.5×4.5mm. Take an appropriate amount of ferric nitrate, dissolve it in 60ml of deionized water by heating, adjust the pH value to 2.5, impregnate the equal volume on the surface of the carrier at the temperature of the impregnating solution at 50°C, flip the carrier quickly and impregnate for 6 minutes, let it rest for 30 minutes until the adsorption equilibrium, and age at 60°C for 30 minutes, then Follow the program in the oven: Dry the catalyst, and then use the temperature programming method to activate the catalyst. The activation procedure: Weigh an appropriate amount of cobalt nitrate, and impregnate according to the above preparation steps.

[0100] Evaluation method:

[0101] Before the catalyst is used, it is reduced with 40% hydrogen + 60% nitrogen in the reduction furnace. The reduction temperature is 300°C and the pressure is 0.5MPa. figure 2 shown. Reduction time 4h. Attached figure 1 In the hydrogenati...

Embodiment 2

[0107] At 50°C, a certain amount of NaAlO 2 solution and ZrCl 4 The solution was stirred and mixed, then neutralized with nitric acid solution, stirred for 10 hours, and uniform Al-Zr particles were formed by co-precipitation. The resultant was filtered and the Na in it was washed with deionized water + and Cl - Ions, and then add an appropriate amount of polyvinyl alcohol with a mass concentration of 15% as a pore-forming agent, and knead it into shape. Dry at 130°C for 2h, and calcined at 650°C for 4h to obtain a Zr-Al composite support. The mass ratio of alumina to zirconia in the carrier is 4:1.

[0108] The catalyst was prepared with alumina-zirconia composite carrier. Take an appropriate amount of ferric chloride and cobalt chloride, heat and dissolve in deionized water, adjust the pH value to 2.0, and impregnate the excess on the carrier at a temperature of 80°C, shake the beaker for 10 minutes, and filter off the excess impregnating liquid. Aging in a water bath ...

Embodiment 3

[0113] Weigh 100ml of a Φ1.5mm spherical α-alumina carrier. Dissolve an appropriate amount of ferric nitrate in 40ml of deionized water, adjust the pH value to 3.0, soak the liquid at a temperature of 40°C, spray the watering can onto the carrier, load it in the drum for 10 minutes to load the active components evenly, and control the loading process to 6 minutes to complete, then Follow the program in the oven: Dry the catalyst, move the catalyst into an evaporating dish, and activate the catalyst in a muffle furnace using a temperature-programmed method. The activation procedure: Obtain a catalyst dip.

[0114] Using the same method as the first step, take an appropriate amount of cobalt nitrate, dissolve it, spray it on the surface of the dipped catalyst, dry it, and roast it to obtain the final catalyst. Drying procedure: The physical properties of the carrier and catalyst, and the content of each component of the catalyst are shown in Table 3.

[0115] Before the...

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Abstract

The invention relates to a selective hydrogenation method for a methanol to olefin product. An Fe-Co hydrogenation catalyst is employed for selective hydrogenation of a C2 and C3 mixture from a dryingtower bottom in an adiabatic bed reactor. The raw material composition includes, by volume, 1.2-1.5% of H2, 0.5-1.0% of N2, 0.005-0.015% of O2, 0.6-1.0% of CO, 0.2-0.6% of CO2, 0-0.0008% of H2S, 6-10% of methane, 1-2% of ethane, 0-0.01% of acetylene, 40-60% of ethylene, 1.5-3% of propane, 15-40% of propylene, 0-0.01% of propyne, 3-6% of C4, and 6-10% of C5 or above. The reaction conditions include: a temperature of 25DEG C-50DEG C, a pressure of 1.5-2.5MPa, and a space velocity of 2000-15000h<-1>. The hydrogenation catalyst carrier is a high temperature resistant inorganic oxide, and the active components at least contain Fe and Co, in terms of a 100% catalyst mass, the catalyst contains 2-6% of Fe and 0.5-1.0% of Co. The catalyst has mild hydrogenation activity and excellent ethylene selectivity, no ethylene loss, low "green oil" production, and much lower cost than a precious metal Pd catalyst.

Description

technical field [0001] The present invention relates to a method for selective hydrogenation of methanol-to-olefins products, in particular to a method for the selective hydrogenation of acetylene, propyne (MA), propadiene (PD) by using iron-based hydrogenation catalysts in methanol-to-olefins products. ) selective hydrogenation method. Background technique [0002] Low-carbon olefins such as ethylene and propylene are important basic chemical raw materials. With the development of my country's national economy, especially the development of modern chemical industry, the demand for low-carbon olefins is increasing day by day, and the contradiction between supply and demand will become increasingly prominent. So far, the important way to produce low-carbon olefins such as ethylene and propylene is still through catalytic cracking and cracking of naphtha and light diesel oil (both from petroleum). As raw materials for ethylene production, naphtha, light diesel oil, etc. Raw m...

Claims

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Application Information

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IPC IPC(8): C07C5/05C07C5/09B01J23/75B01J35/10C07C11/04C07C11/06
CPCC07C5/05C07C5/09B01J23/75C07C2523/75B01J35/612B01J35/613B01J35/615B01J35/635B01J35/633C07C11/04C07C11/06Y02P20/52
Inventor 钱颖张峰谷丽芬车春霞韩伟梁玉龙何崇慧景喜林苟尕莲潘曦竹景丽杨珊珊郭珺
Owner PETROCHINA CO LTD
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