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Coupled catalyst system used for directly producing light olefins with synthetic gas

A low-carbon olefin and synthesis gas technology, applied in molecular sieve catalysts, physical/chemical process catalysts, hydrocarbon production from carbon oxides, etc. Sexual problems, etc.

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

[0014] The purpose of the present invention is to solve the problems of poor sulfur resistance of the catalyst in the prior art, low selectivity of low-carbon olefins in the product and non-adjustable ratio of ethylene / propylene, and to provide a new method for producing low-carbon olefins from syngas Coupled catalytic system, which has the advantages of strong sulfur resistance, high selectivity of low-carbon olefins and adjustable ratio of ethylene to propylene when used in the reaction of syngas to light olefins

Method used

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  • Coupled catalyst system used for directly producing light olefins with synthetic gas
  • Coupled catalyst system used for directly producing light olefins with synthetic gas

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Mo-Fe 0.6 Zn 0.2 Cs 0.8 Sulfide catalyst is prepared as follows:

[0039] Weigh 0.05 mol of ammonium thiomolybdate and dissolve in water, weigh 0.03 mol of ferric nitrate and 0.01 mol of zinc nitrate and dissolve in water, and co-precipitate the two aqueous solutions in parallel, filter and wash after precipitation. Dry overnight and bake at 500°C for 4h. Sulfide intermediate loaded with 0.02mol of Cs 2 CO 3 , dried overnight at 80°C and calcined at 400°C for 1h to obtain Mo-Fe 0.6 Zn 0.2 Cs 0.8 Sulfide catalyst.

[0040] The SAPO-34 catalyst is prepared according to the following steps: phosphoric acid, pseudoboehmite, ethyl orthosilicate, and morpholine are respectively used as phosphorus source, aluminum source, silicon source, template agent, and the molar ratio Al 2 o 3 :P 2 o 5 : SiO 2 :R:H 2 O=1:1:0.6:3:100, add to the reactor and age for 2 hours, stir and crystallize at 200°C for 24 hours, wash the obtained solid with deionized water until neutral,...

Embodiment 2

[0043] Mo-Fe 0.8 Cs 0.8 Sulfide catalyst is prepared as follows:

[0044] Weigh 0.05mol of ammonium thiomolybdate and dissolve in water, weigh 0.04mol of ferric nitrate and dissolve in water, and co-precipitate the two aqueous solutions in parallel, filter and wash after precipitation, dry at 100°C overnight, and dry at 500°C Under roasting 4h. Sulfide intermediate loaded with 0.02mol of Cs 2 CO 3 , dried overnight at 80°C and calcined at 400°C for 1h to obtain Mo-Fe 0.8 Cs 0.8 Sulfide catalyst.

[0045] The SAPO-34 catalyst was prepared according to [Example 1].

[0046] 0.75 g of prepared Mo-Fe 0.8 Cs 0.8 The sulfide catalyst was mixed with 0.75 gram of prepared SAPO-34, and packed into a quartz reaction tube with an inner diameter of 6 mm, and (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 2,000h -1 The reaction of syngas to l...

Embodiment 3

[0048] Mo-Zn 0.8 Cs 0.8 Sulfide catalyst is prepared as follows:

[0049] Weigh 0.05mol of ammonium thiomolybdate and dissolve in water, weigh 0.04mol of zinc nitrate and dissolve in water, and co-precipitate the two aqueous solutions in parallel, filter and wash after precipitation, dry at 100°C overnight, and then dry at 500°C Under roasting 4h. Sulfide intermediate loaded with 0.02mol of Cs 2 CO 3 , dried overnight at 80°C and fired at 400°C for 1h to obtain Mo-Zn 0.8 Cs 0.8 Sulfide catalyst.

[0050] The SAPO-34 catalyst was prepared according to [Example 1].

[0051] 0.75 g of prepared Mo-Zn 0.8 Cs 0.8 The sulfide catalyst was mixed with 0.75 gram of prepared SAPO-34, and packed into a quartz reaction tube with an inner diameter of 6 mm, and (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 2,000h -1 The reaction of syngas to l...

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Abstract

The invention belongs to the technical field of chemistry and chemical engineering and particularly provides a coupled catalyst system used for directly producing light olefins with synthetic gas. Theinvention mainly solves the problem of low selectivity on the light olefins of a catalyst used for preparing light olefins with synthetic gas in the prior art. In the catalyst, a synthetic gas-to-alcohol catalyst and an alcohol-to-olefin catalyst are coupled to achieve the one-step process of directly producing olefins with synthetic gas. The synthetic gas-to-alcohol catalyst is a modified molybdenum-based catalyst had has the molecular general formula of MoTt-XaYbZc, wherein T is at least one selected from S, O or C, the X is one or more of Fe, Co, Ni, Ru, Rh and Pd; the Y is one or more ofCr, Mn, Zn, La, Ce; the Z is one or more selected from alkali metals. The alcohol-to-olefin catalyst is a molecular sieve having a CHA skeleton structure. The catalyst solves the mentioned problems well, can product C2-C4 olefin products high-effectively, continuously and stably, and can be used for industrial production of preparing light olefins with synthetic gas.

Description

technical field [0001] The invention belongs to the technical field of chemistry and chemical engineering, and in particular relates to a coupled catalyst system for direct production of low-carbon olefins from synthesis gas, in particular to a coupled catalyst system for efficient direct production of ethylene and propylene from synthesis gas. Background technique [0002] Low-carbon olefins (such as ethylene and propylene) are important chemical raw materials. With the growth of the national economy, their consumption demand is also increasing. Although the production of ethylene and propylene in my country has a considerable scale, the self-sufficiency rate of consumption is low, and the contradiction between supply and demand is still very prominent. With the dwindling of petroleum resources, coal and natural gas will gradually replace petroleum as new sources of fuel and chemical raw materials. market. [0003] Due to the resource endowment of rich coal, lack of oil a...

Claims

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Application Information

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IPC IPC(8): B01J29/85C07C1/04C07C11/04C07C11/06C07C11/08
CPCY02P20/52
Inventor 周海波刘苏刘畅苏俊杰王仰东
Owner CHINA PETROLEUM & CHEM CORP
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