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A kind of cobalt-based Fischer-Tropsch synthesis heavy hydrocarbon catalyst and its preparation method and application

A Fischer-Tropsch synthesis and catalyst technology, which is used in catalyst activation/preparation, chemical instruments and methods, and preparation of liquid hydrocarbon mixtures, etc., can solve the problems of undisclosed heavy hydrocarbon selectivity, high carrier price, etc., and achieves improved catalytic activity. and selectivity, beneficial to diffusion, and the effect of improving activity

Active Publication Date: 2021-04-30
XIAN ORIGIN CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Patent No. CN 1398951 discloses a Co / TiO2 for Fischer-Tropsch synthesis of heavy hydrocarbons 2 Catalyst with high CO conversion rate, C 1 The selectivity is 7.7~18.8%, C 5 +Selectivity 68.3~85.9%, but heavy hydrocarbon selectivity is not mentioned, and TiO 2 Carriers are more expensive
The disclosed adopting ZrO of CN1401736 2 The cobalt-based Fischer-Tropsch synthesis catalyst used as a carrier also has the problem that the carrier price is relatively expensive, and the C 19 + Selectivity for heavy hydrocarbons

Method used

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  • A kind of cobalt-based Fischer-Tropsch synthesis heavy hydrocarbon catalyst and its preparation method and application
  • A kind of cobalt-based Fischer-Tropsch synthesis heavy hydrocarbon catalyst and its preparation method and application
  • A kind of cobalt-based Fischer-Tropsch synthesis heavy hydrocarbon catalyst and its preparation method and application

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Experimental program
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Effect test

Embodiment 1

[0040] The catalyst of this embodiment is made up of the composition of following mass percentage: 15% cobalt, 0.1% rhenium, all the other are gamma-Al 2 o 3 carrier; the γ-Al 2 o 3 The pore size of the carrier is 14nm and the specific surface area is 280m 2 / g, the pore volume is 0.80mL / g.

[0041] The preparation method of the catalyst of the present embodiment comprises the following steps:

[0042] Step 1. Add 0.254mol cobalt nitrate hexahydrate and 0.127mol citric acid into deionized water to prepare a mixed solution, then add 1.4mL of perrhenic acid whose rhenium concentration is 71.4g / L, and dilute to 130mL with deionized water, Obtain an impregnation solution;

[0043] Step 2: Spray 65mL impregnating solution evenly onto 84.9g of γ-Al 2 o 3 On the carrier, impregnate equal volume at room temperature for 3.5h, and then dry at 70°C for 6h;

[0044] Step 3, the dried γ-Al in step 2 2 o 3 The carrier was calcined at 210°C for 1 hour, then heated to 300°C for 5 ho...

Embodiment 2

[0047] The catalyst of this embodiment is made up of the composition of following mass percentage: 18% cobalt, 0.3% rhenium, all the other are gamma-Al 2 o 3 carrier; the γ-Al 2 o 3 The pore size of the carrier is 12nm and the specific surface area is 300m 2 / g, the pore volume is 0.65mL / g.

[0048] The preparation method of the catalyst of the present embodiment comprises the following steps:

[0049] Step 1. Add 0.305 mol of cobalt acetate and 0.183 mol of citric acid into deionized water to prepare a mixed solution, then add 4.2 mL of perrhenic acid with a rhenium concentration of 71.4 g / L, and dilute to 120 mL with deionized water to obtain impregnation liquid;

[0050] Step 2: Spray 60mL impregnating solution evenly onto 81.7g of γ-Al 2 o 3 On the carrier, impregnate equal volume at room temperature for 2 hours, and then dry at 60°C for 8 hours;

[0051] Step 3, the dried γ-Al in step 2 2 o 3 The carrier was calcined at 190°C for 3 hours, then heated to 330°C fo...

Embodiment 3

[0054] The catalyst of this embodiment is made up of the composition of following mass percentage: 20% cobalt, 0.2% rhenium, all the other are gamma-Al 2 o 3 carrier; the γ-Al 2 o 3 The pore size of the carrier is 23nm and the specific surface area is 185m 2 / g, the pore volume is 1.00mL / g.

[0055] The preparation method of the catalyst of the present embodiment comprises the following steps:

[0056] Step 1. Add 0.339mol of cobalt acetate tetrahydrate and 0.271mol of ammonium ethylenediaminetetraacetate into deionized water to prepare a mixed solution, then add 4mL of ammonium perrhenate solution with rhenium concentration of 50g / L, and use deionized water Dilute to 140mL to obtain impregnation solution;

[0057] Step 2: Evenly spray 70mL impregnating liquid onto 79.8g of γ-Al 2 o 3 On the carrier, impregnate equal volume at room temperature for 5.5h, and then dry at 80°C for 5h;

[0058] Step 3, the dried γ-Al in step 2 2 o 3 The carrier is calcined at 200°C for 2...

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Abstract

The invention discloses a cobalt-based Fischer-Tropsch synthesis heavy hydrocarbon catalyst, which comprises 15%-25% cobalt, 0.04%-0.3% rhenium and γ-Al 2 o 3 carrier. Catalyst of the present invention is γ-Al with larger pore diameter, specific surface and pore volume 2 o 3 As a carrier, cobalt particles of moderate size are formed, which is beneficial to material transfer and improves the selectivity of heavy hydrocarbons. The invention also discloses a method for preparing the catalyst. In the method, cobalt salt, dispersant and rhenium liquid are prepared into impregnating liquid, and then impregnated into γ-Al 2 o 3 carrier, and then dried, calcined and cooled to obtain the catalyst. The invention improves the uniformity of cobalt dispersion and improves the activity and selectivity of the catalyst through the method of two-step impregnation and adding a dispersant. The invention also discloses a Fischer-Tropsch synthesis method, which adopts temperature-programmed reduction in stages, avoids sintering or agglomeration of catalyst particles, is beneficial to the stability of catalyst morphology, and prolongs the service life of the catalyst.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and in particular relates to a cobalt-based Fischer-Tropsch synthesis heavy hydrocarbon catalyst and its preparation method and application. Background technique [0002] Fischer-Tropsch synthesis is a process of converting synthesis gas into hydrocarbons through a catalytic reaction, through which mixed hydrocarbons and some oxygenated compounds can be obtained, so Fischer-Tropsch synthesis has received extensive attention and research. Since the products of Fischer-Tropsch synthesis are complex and distributed in ASF (Anderson-Shulz-Flory), under the premise of ensuring the high activity of the catalyst, adjusting the product distribution and obtaining a certain fraction of products with high selectivity is the research goal of Fischer-Tropsch synthesis catalysts. one of the core issues. The production cost of Fischer-Tropsch synthesis is relatively high. From the perspective of commercial i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/889B01J37/02C10G2/00
CPCB01J23/8896B01J37/0205C10G2/332C10G2300/70
Inventor 张睿潘喜强齐小峰潘蕊娟王红梅谢小莉段超
Owner XIAN ORIGIN CHEM TECH
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