Copper catalyst for selective hydrogenation of mixed C4 and preparation method of copper catalyst

A technology for selective hydrogenation and copper catalysts, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc.

Active Publication Date: 2013-06-26
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In today's high price of butadiene, the large l

Method used

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  • Copper catalyst for selective hydrogenation of mixed C4 and preparation method of copper catalyst
  • Copper catalyst for selective hydrogenation of mixed C4 and preparation method of copper catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Weigh 38g of Cu(NO 3 ) 2· 3H 2 O, 0.79g of AgNO 3 and 9.9g of Co(NO 3 ) 2· 6H 2 O, measure butylamine 38.2mL, make the ratio of butylamine and Cu, Ag, Co total mole number be 2: 1, butylamine and 30mL water are mixed uniformly, then Cu(NO 3 ) 2· 3H 2 O, AgNO 3 and Co(NO 3 ) 2· 6H 2 O is added to the aqueous solution of butylamine to dissolve evenly, and it is made into an impregnating solution.

[0021] Weigh 87.5gAl 2 o 3 Tooth ball carrier, its specific surface is 197m 2 / g, the pore volume is 0.6mL / g. Spray the above impregnating solution on the Al 2 o 3 Carrier, then aged for 5 hours, dried at 120°C for 10 hours, and calcined at 400°C for 4 hours to finally obtain Catalyst A. The content of Cu in catalyst A is 10wt%, the content of Ag is 0.5wt%, and the content of Co is 2wt%.

Embodiment 2

[0026] Weigh 38g of Cu(NO 3 ) 2· 3H 2 O, 9.9g of Ni(NO 3 ) 2· 6H 2 O, 4.6g 50% Mn(NO 3 ) 2 solution, 3.8gCr(NO 3 ) 3 9H 2 O, 0.32g of AgNO 3 and 4.9g of Co(NO 3 ) 2· 6H 2 O. Measure 21.9 mL of diethanolamine, so that the ratio of diethanolamine to the total moles of Cu, Ni, Mn, Cr, Ag, Co is 1:1, mix diethanolamine and 35 mL of water evenly, and then mix Cu(NO 3 ) 2· 3H 2 O, Ni(NO 3 ) 2· 6H 2 O, Mn(NO 3 ) 2 , Cr(NO 3 ) 3 9H 2 O, AgNO 3 , Co(NO 3 ) 2· 6H 2 O is dissolved in an aqueous solution of diethanolamine to prepare an impregnating solution.

[0027] Weigh 85.8gAl 2 o 3 Small ball carrier, its specific surface is 115m 2 / g, the pore volume is 0.5mL / g. Spray the above impregnating solution on the Al 2 o 3 Carrier, then aged for 5 hours, dried at 120°C for 10 hours, and calcined at 400°C for 4 hours to finally obtain Catalyst B. Cu content is 10wt% in the catalyst B, and Ni content is 2wt%, and Mn content is 0.5wt%, and Cr content is 0.5wt...

Embodiment 3

[0032] The present embodiment evaluates the catalyst of the present invention, and the test conditions are as follows:

[0033] The catalyst test was carried out in a fixed bed reactor with a catalyst loading of 200mL. Before the reaction, it must be replaced with nitrogen and then reduced with hydrogen at 250°C for 4 hours. The composition of the mixed C4 raw materials is listed in Table 1. Flow through the reactor from bottom to top, the catalyst bed inlet temperature is 30-60°C, the reaction pressure is 1.0MPa, and the liquid space velocity of the C4 fraction is 4h -1 , The molar ratio of hydrogen to alkyne (often referred to as hydrogen-alkyne ratio) is 2-4.

[0034] Calculation Method of Residual Alkyne and Butadiene Loss in Reaction

[0035] 1. Calculation of remaining total alkynes:

[0036] Total alkynes remaining = VA remaining in reaction + EA remaining in reaction + MA remaining in reaction

[0037] 2. Calculation of butadiene loss:

[0038] Butadiene loss wt% =...

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Abstract

The invention discloses a copper catalyst for selective hydrogenation of mixed C4 and a preparation method of the copper catalyst. The copper catalyst comprises an alumina carrier, 5-50% of active component (Cu), and 0.1-20% of an assistant (one or more of Ag, Co, Fe, Mn, Ni, Zn, Cr and Pd). In the preparation process of the catalyst, organic amine is added to be subjected to complexing with a metal component to effectively improve the uniformity and the dispersibility of alloy formed on the surface of the catalyst. The copper catalyst is used for the process of removing alkyne through selective hydrogenation by the mixed C4, and has good selectivity and long operation cycle.

Description

technical field [0001] The invention relates to a selective hydrogenation catalyst and a preparation method thereof. Specifically, the present invention relates to a hydrogenation catalyst with a uniform and highly dispersed copper alloy as an active component, which is especially suitable for the selective hydrogenation and removal of alkyne from the cracking carbon four fraction to produce butadiene. Background technique [0002] At present, the two-stage extraction and two-stage rectification process is the mainstream method for producing 1,3-butadiene. In the 1980s, DOW introduced the selective hydrogenation process into the production of butadiene, that is, KLP technology. The catalyst used was Cu as the active component, and some additives were added to improve the selectivity of the Cu catalyst. Its representative patent is US4101451. The selectivity of the Cu catalyst is good, but the main problem is that the single operation period is short and frequent regeneratio...

Claims

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Application Information

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IPC IPC(8): B01J23/89C07C11/16C07C7/167
Inventor 杨栋戴伟朱云仙乐毅徐立英
Owner CHINA PETROLEUM & CHEM CORP
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