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Combined catalyst used for preparing light olefins and use method thereof

A technology of combining catalysts and carbon olefins, applied in molecular sieve catalysts, chemical instruments and methods, catalyst activation/preparation, etc., can solve problems such as large fixed investment, low selectivity, and complex reaction devices

Active Publication Date: 2019-05-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] CN1683079A relates to a catalyst for the reaction of methanol to olefins, which mainly solves the problem of low catalyst activity, low selectivity of ethylene, propylene and butene, low selectivity of ethylene, propylene and butene, and low ethylene and the problem of low yield of propylene
[0010] In summary, although some of the existing technologies have a high CO conversion rate, the selectivity of olefins, especially the selectivity of low-carbon olefins, is low, which is far from the ideal goal of industrial application; some adopt two-step In this method, syngas needs to be converted into methanol first, and then converted into light olefins. This technology has high selectivity, but the conversion path required for the two-step reaction is long, the reaction device is complicated, and the intermediate product / product needs to be separated many times. , large fixed investment, high consumption of energy and materials

Method used

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  • Combined catalyst used for preparing light olefins and use method thereof
  • Combined catalyst used for preparing light olefins and use method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] ZnCr 0.8 Catalyst is prepared as follows:

[0042] Weigh 1 mol of zinc nitrate and 0.8 mol of chromium nitrate, dissolve them in 1000 mL of distilled water, then dissolve 5 mol of NaOH in 1000 mL of water, co-precipitate the two aqueous solutions, age at 70°C for 3 hours, and filter at 100°C Dry overnight at 400°C and bake at 400°C for 12 hours to obtain ZnCr 0.8 catalyst.

[0043] AlPO 4 -5 catalyst is prepared as follows:

[0044] Pseudoboehmite, phosphoric acid, and tri-n-propylamine (TPA) were used as aluminum source, phosphorus source, and template agent respectively, and the molar ratio of Al 2 o 3 :P 2 o 5 :TPA:Ethanol:H 2 O=1:1.2:2.66:80:1000, add to the reactor and age for 2 hours, stir and crystallize at 190°C for 48 hours, wash the obtained solid with deionized water until neutral, separate the solid, dry it, and put it in a muffle furnace Calcined at 550°C for 6 hours to obtain AlPO 4 -5 molecular sieves.

[0045] 0.75 g of prepared ZnCr 0.8 Cata...

Embodiment 2

[0047] ZnCr 0.8 Al 0.2 Catalyst is prepared as follows:

[0048] Weigh 1 mol of zinc nitrate, 0.8 mol of chromium nitrate, 0.2 mol of aluminum nitrate, dissolve in 1000 mL of distilled water, then dissolve 5 mol of NaOH in 1000 mL of water, co-precipitate the two aqueous solutions, and age at 70 ° C for 3 hours , dried overnight at 100°C after filtration, and calcined at 400°C for 12h to obtain ZnCr 0.8 Al 0.2 catalyst.

[0049] AlPO 4 -5 Catalyst is prepared by [embodiment 1].

[0050] 0.75 g of prepared ZnCr 0.8 Al 0.2 Catalyst and 0.75 g of prepared AlPO 4 -5 mixed, packed into a quartz reaction tube with an inner diameter of 6 mm, the (n 氢气 :n 一氧化碳 =50:50) into the reaction tube, into the catalytic bed reaction, the reaction temperature is 400 ℃, the reaction system pressure is 4MPa, the gas volume space velocity is 4,000h -1 The reaction of syngas to light olefins is carried out under the conditions. The activity evaluation results are shown in Table 1.

Embodiment 3

[0052] ZnCr 0.8 Al 0.2 -K 0.1 Catalyst is prepared as follows:

[0053] Weigh 1 mol of zinc nitrate, 0.8 mol of chromium nitrate, 0.2 mol of aluminum nitrate, dissolve in 1000 mL of distilled water, then dissolve 5 mol of NaOH in 1000 mL of water, co-precipitate the two aqueous solutions, and age at 70 ° C for 3 hours , dried overnight at 100°C after filtration, and calcined at 400°C for 12h. After the calcination is completed, the catalyst intermediate is loaded with 0.05 mol of K 2 CO 3 , dried overnight at 80°C, and fired at 400°C for 1 hour to obtain ZnCr 0.8 Al 0.2 -K 0.1 catalyst.

[0054] AlPO 4 -5 Catalyst is prepared by [embodiment 1].

[0055] 0.75 g of prepared ZnCr 0.8 Al 0.2 -K 0.1 Catalyst and 0.75 g of prepared AlPO 4 -5 mixed, packed into a quartz reaction tube with an inner diameter of 6 mm, the (n 氢气 :n 一氧化碳 =50:50) into the reaction tube, into the catalytic bed reaction, the reaction temperature is 400 ℃, the reaction system pressure is 4MPa,...

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Abstract

The invention belongs to the technical field of chemistry and chemical engineering and particularly provides a combined catalyst used for preparing light olefins from synthetic gas and a use method thereof, and mainly solves the problem that a catalyst used for preparing light olefins from synthetic gas is low in selectivity in the prior art. In the catalyst, an ZnCr oxide catalyst is coupled witheight-membered ring, ten-membered ring and twelve-membered ring molecular sieve catalysts containing P and Al, wherein the ZnCr oxide catalyst has the molecular general formula of ZnCrXY<c>O<d>. The catalyst achieves direct production of olefins from the synthetic gas in one step, solves the problems well, can be used for preparing C2-C4 olefins high-effectively, continuously and stably, and can be used for industrial production of preparing light olefins from synthetic gas.

Description

technical field [0001] The invention belongs to the technical field of chemistry and chemical engineering, and specifically relates to a combined catalyst for producing low-carbon olefins, in particular to a combined catalyst for directly producing low-carbon olefins with high selectivity from synthesis gas and a preparation method thereof. Background technique [0002] Low-carbon olefins represented by ethylene and propylene are important standards for measuring the level of a country's chemical industry, and are also important organic chemical raw materials, which can produce bulk synthetic materials such as plastics, synthetic resins, fibers, and rubber. In recent years, the production capacity of low-carbon olefins in my country has continued to increase, and the production has reached a considerable scale, but the import volume has continued to grow for a long time. In 2011, my country's ethylene and propylene production reached 15.275 million tons and 14.530 million to...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/84B01J29/85B01J37/03B01J37/08C07C11/04C07C11/06C07C1/04
CPCY02P20/52
Inventor 周海波刘苏刘红星赵昱王仰东滕加伟刘畅苏俊杰
Owner CHINA PETROLEUM & CHEM CORP
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