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A method for removing alkyne by hydrogenation before depropanization

A pre-depropanizer and pre-hydrogenation technology, applied in chemical instruments and methods, hydrogenation to hydrocarbons, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problem of high reaction temperature, harsh conditions, and acetylene conversion rate Low-level problems, to achieve the effect of good ethylene selectivity, good operating flexibility and moderate reactivity

Active Publication Date: 2019-11-08
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
[0024] 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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  • A method for removing alkyne by hydrogenation before depropanization
  • A method for removing alkyne by hydrogenation before depropanization
  • A method for removing alkyne by hydrogenation before depropanization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0080] Weigh a clover-shaped alumina carrier of Φ4.5×4.5mm. Take 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 50°C, flip the carrier quickly for 6 minutes, let it stand still for 30 minutes until the adsorption equilibrium, and age at 60°C for 30 minutes, then in In the oven follow the procedure: Dry the catalyst, and then use the temperature programming method to activate the catalyst. The activation procedure: Weigh lanthanum nitrate and impregnate according to the above preparation steps.

[0081] Before the catalyst is used, it is reduced with 40% hydrogen + 60% nitrogen in a reduction furnace, the reduction temperature is 300° C., the pressure is 0.5 MPa, and the reduction time is 4 hours. Attached figure 1 In the hydrogenation process shown, the catalyst is packed in an adiabatic bed reactor.

[0082] The composition of the reaction ma...

Embodiment 2

[0088] At 50°C, the 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 polyvinyl alcohol with a mass concentration of 15% as a pore-forming agent, kneading and molding. 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.

[0089] The catalyst was prepared with alumina-zirconia composite carrier. Take ferric chloride and potassium chloride, heat and dissolve them in deionized water, adjust the pH value to 2.0, impregnate the excess on the carrier at a temperature of 80°C, shake the beaker for 10 minutes, filter off the excess impregnating liquid, and place the catalyst in a water bath at 60°C Medium aging for 50min, then follow the proc...

Embodiment 3

[0095] The spherical alumina of Φ1.5 mm was weighed to prepare the catalyst. Dissolve ferric nitrate in deionized water, adjust the pH value to 3.0, soak the solution at a temperature of 40°C, spray it on the carrier with a watering can, load it for 10 minutes to make the active components evenly loaded, and then follow the procedure in the oven: Dry the catalyst, and use the temperature programming method to activate the catalyst. The activation procedure: Obtain a catalyst dip.

[0096] Using the same method as the first step, take cerium nitrate, dissolve it, spray it on the surface of the catalyst, dry it, and roast it to obtain the final catalyst. Drying procedure: Roasting procedure:

[0097] Before the catalyst is used, it is reduced with 20% hydrogen in a reduction furnace, the reduction temperature is 340° C., the pressure is 0.5 MPa, and the reduction time is 4 hours. Catalyst XRD analysis after reduction is attached figure 2 shown. Attached figure 1 I...

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Abstract

A method for removing acetylene by hydrogenation before depropanization. The volume composition of hydrogenation raw materials is mainly: methane 30~40%, hydrogen 15-25%, ethane 8~15%, ethylene 30~45%, propane 5~10%, propylene 5~10%, and allene 0.1~ 0.5%, acetylene 0.5~1.0%, propyne 0.1~0.5%. The reaction conditions are: the inlet temperature of the first stage is 50~100℃, the inlet temperature of the second stage is 50~100℃, the inlet temperature of the third stage is 50~100℃, the reaction pressure is 1.5~4.0MPa, and the reaction volume space velocity is 10000~20000h. ‑1 . The hydrogenation catalyst is an Fe-based selective hydrogenation catalyst, and the carrier is a high-temperature resistant inorganic oxide. Using the acetylene removal method of the present invention, the catalyst has moderate reaction activity, good operating flexibility, good ethylene selectivity, and the amount of "green oil" generated is much lower than that of precious metals. catalyst.

Description

technical field [0001] The invention relates to a method for removing alkyne by hydrogenation before depropanization, in particular to a Fe-based hydrogenation catalyst for hydrogenation of ethylene, propylene (MA) and propadiene (MA) contained in hydrogenation ethylene materials before depropanization A method of converting hydrogen into propylene and allene. Background technique [0002] The production of polymer grade ethylene is the leader of the petrochemical industry, and polymer grade ethylene and propylene are the most basic raw materials for downstream polymerization units. Among them, the selective hydrogenation of acetylene has an extremely important impact on the ethylene processing industry. In addition to ensuring that the acetylene content at the outlet of the hydrogenation reactor reaches the standard, the selectivity of the catalyst is excellent, which can make ethylene generate as little ethane as possible, which is beneficial to improving the entire proces...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C5/09C07C11/04C07C11/06B01J23/83B01J23/78B01J23/745
CPCC07C5/09B01J23/002B01J23/745B01J23/78B01J23/83C07C2523/83C07C2523/78C07C2523/745B01J35/613B01J35/633B01J35/635B01J35/615C07C11/04C07C11/06Y02P20/52
Inventor 韩伟梁玉龙张峰钱颖蔡小霞潘曦竹车春霞苟尕莲景喜林杨珊珊郭珺景丽
Owner PETROCHINA CO LTD
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