Catalyst and method for direct conversion of syngas to light olefins

Patent metadata

Field	Value
Publication number	US-10960387-B2
Application number	US-201716463142-A
Country	US
Kind code	B2
Filing date	Dec 4, 2017
Priority date	Dec 5, 2016
Publication date	Mar 30, 2021
Grant date	Mar 30, 2021

Abstract

Direct conversion of syngas to light olefins is carried out in a fixed bed or a moving bed reactor with a composite catalyst A+B. The active ingredient of catalyst A is active metal oxide; and catalyst B is one or more than one of zeolite of CHA and AEI structures or metal modified CHA and/or AEI zeolite. A spacing between geometric centers of the active metal oxide of the catalyst A and the particle of the catalyst B is 5 μm-40 mm. A spacing between axes of the particles is preferably 100 μm-5 mm, and more preferably 200 μm-4 mm. A weight ratio of the active ingredients in the catalyst A and the catalyst B is within a range of 0.1-20 times, and preferably 0.3-5.

First claim

We claim:

1. A catalyst, comprising a metal oxide chosen from MnO, MnCr 2 O 4 , MnAl 2 O 4 , MnZrO 4 , ZnO, ZnAl 2 O 4 , CoAl 2 O 4 , FeAl 2 O 4 , or mixtures thereof, and a zeolite of CHA and/or AEI topology.

2. The catalyst of claim 1 , wherein the zeolite has a skeleton comprising species chosen from Si—O, Si—Al—O, Si—Al—P—O, Al—P—O, Ga—P—O, Ga—Si—Al—O, Zn—Al—P—O, Mg—Al—P—O, or Co—Al—P—O.

3. The catalyst according to claim 1 , wherein the zeolite has an amount of medium-strength acid sites of 0-0.3 mol/kg, wherein the medium-strength acid sites are characterized by a peak temperature range corresponding to a desorption peak of NH3-TPD of 275-500° C., and a chemical shift of 13 C-NMR in a range of 210-220 ppm using acetone as a probe molecule.

4. The catalyst according to claim 1 , wherein the metal oxide and the zeolite are particles, wherein when a particle of the metal oxide and a particle of the zeolite are adjacent to each other, a spacing between a geometric center of the metal oxide particle and a geometric center of the adjacent zeolite particle is in a range of 5 μm-40 mm.

5. The catalyst according to claim 1 , wherein a weight ratio between the metal oxide and the zeolite is in a range of 0.1-20.

6. The catalyst according to claim 1 , wherein the metal oxide is composed of crystal grains with a size of 5-30 nm, and wherein each crystal grain has oxygen vacancies within a distance of 0.3 nm from a surface thereof to at a molar concentration of 20%-80%, wherein the molar concentration is a percentage of a mole number the oxygen vacancies and a mole number of a theoretical amount of oxygen atoms.

7. The catalyst according to claim 1 , further comprising a dispersing agent chosen from Al 2 O 3 , SiO 2 , Cr 2 O 3 , ZrO 2 , TiO 2 or mixtures thereof, wherein the metal oxide is dispersed in the dispersing agent and a weight percentage of the dispersing agent in the metal oxide is 0.05-90 wt %.

8. The catalyst according to claim 1 , wherein, on the skeleton of the zeolite, at least a portion of H in hydroxyl groups are substituted by one or more metal chosen from Na, Ca, K, Mg, Ge, Zr, Zn, Cr, Ga, Sn, Fe, Co, Mo, or Mn by ion exchange, and a total molar ratio of the substitute metal to oxygen is 0.0002-0.001.

9. A method for preparing light olefins using direct conversion of syngas, comprising contacting syngas with the catalyst of claim 1 , wherein a pressure of syngas is 0.5-10 MPa, a reaction temperature is 300-600° C., a space velocity is 300-10000 h −1 , and a molar ratio between H 2 and CO in the syngas 0.2-3.5.

10. The catalyst according to claim 2 , wherein the zeolite has medium-strength acid sites of 0.003-0.2 mol/kg, wherein the medium-strength acid sites are characterized by a peak temperature range corresponding to a desorption peak of NH3-TPD for medium-strength acid of 275-500° C., and a chemical shift of 13 C-NMR in a range of 210-220 ppm using acetone as a probe molecule.

11. The catalyst according to claim 5 , wherein, on the skeleton of the zeolite, at least a portion of H in hydroxyl groups are substituted by one or more metal chosen from Na, Ca, K, Mg, Ge, Zr, Zn, Cr, Ga, Sn, Fe, Co, Mo, Mn, or mixtures thereof by ion exchange, and a total molar ratio of the substitute metal to oxygen is 0.0002-0.001.

12. The catalyst of claim 2 , wherein a molar ratio of Si:Al, Si:(Ga+Al), Zn:Al, Mg:Al, or Co:Al in the skeleton of component B is 0.001 to 0.6.

13. The catalyst of claim 2 , wherein the molar ratio of Si:Al, Si:(Ga+Al), Zn:Al, Mg:Al, or Co:Al in the skeleton of component B is 0.001 to 0.48.

14. A catalyst comprising ZnCr 2 O 4 and a zeolite of AEI topology.

15. The catalyst of claim 14 , wherein the zeolite has a skeleton comprising species chosen from Si—O, Si—Al—O, Si—Al—P—O, Al—P—O, Ga—P—O, Ga—Si—Al−O, Zn—Al—P—O, Mg—Al—P—O, or Co—Al—P—O.

16. The catalyst according to claim 14 , wherein ZnCr 2 O 4 and the zeolite are particles, wherein when a particle of ZnCr 2 O 4 and a particle of the zeolite are adjacent to each other, a spacing between a geometric center of the ZnCr 2 O 4 particle and a geometric center of the adjacent zeolite particle is in a range of 5 μm-40 mm.

17. The catalyst according to claim 14 , wherein a weight ratio between ZnCr 2 O 4 and the zeolite is in a range of 0.1-20.

18. A method for preparing light olefins using direct conversion of syngas, comprising contacting syngas with the catalyst of claim 14 , wherein a pressure of syngas is 0.5-10 MPa, a reaction temperature is 300-600° C., a space velocity is 300-10000 h −1 , and a molar ratio between H 2 and CO in the syngas 0.2-3.5.

19. A catalyst comprising ZnCr 2 O 4 and a zeolite of CHA topology, wherein the zeolite has a skeleton comprising species chosen from Si—O, Si—Al—O, Si—Al—P—O, Al—P—O, Ga—P—O, Ga—Si—Al—O, Zn—Al—P—O, Mg—Al—P—O, or Co—Al—P—O, wherein the zeolite has an amount of medium-strength acid sites of 0-0.3 mol/kg, wherein the medium-strength acid sites are characterized by a peak temperature range corresponding to a desorption peak of NH 3 -TPD of 275-500° C. and a chemical shift of 13 C-NMR in a range of 210-220 ppm using acetone as a probe molecule.

20. The catalyst according to claim 19 , wherein ZnCr 2 O 4 and the zeolite are particles, wherein when a particle of ZnCr 2 O 4 and a particle of the zeolite are adjacent to each other, a spacing between a geometric center of the ZnCr 2 O 4 particle and a geometric center of the adjacent zeolite particle is in a range of 5 μm-40 mm.

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Bao Xinhe
• Jiao Feng
• Pan Xiulian
• Ding Minzheng

Classifications

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title

• B01J29/7049

  containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead · CPC title

• B01J29/85

  Silicoaluminophosphates [SAPO compounds] · CPC title