Catalytic reactor configuration, preparation and method of direct synthesis of ethylene through oxygen-free catalysis of methane

Patent metadata

Field	Value
Publication number	US-10661239-B2
Application number	US-201716300188-A
Country	US
Kind code	B2
Filing date	Mar 22, 2017
Priority date	Apr 29, 2016
Publication date	May 26, 2020
Grant date	May 26, 2020

Abstract

A reactor configuration comprises an inlet section I, a preheating section II, a transition section III, a reaction section IV and an outlet section V; except for the preheating section II and the reaction section IV, the existence of the inlet section I, the transition section III and the outlet section V depends on reaction conditions; and the process realizes no coke deposition synthesis of methane and high selectivity synthesis of ethylene. The methane conversion rate is 20-90%; ethylene selectivity is 65-95%; propylene and butylene selectivity is 5-25%; aromatic hydrocarbon selectivity is 0-30%; and coke deposition is zero.

First claim

We claim:

1. A catalytic reactor, comprising a preheating section and a reaction section, wherein the reaction section comprises a quartz tube or a silica carbide tube, wherein the quartz tube or the silica carbide tube has an inner wall that is directly lattice-doped with a catalytically active component or coated with a Si-based material, wherein the Si-based material is lattice-doped by the catalytically active component, to form a dopant thin layer, whereby a feed raw material enters the preheating section first before entering the reaction section.

2. The catalytic reactor according to claim 1 , wherein the length II of the preheating section and the length IV of the reaction section are respectively 50-2000 mm.

3. The catalytic reactor configuration according to claim 1 , wherein the thickness of the dopant thin layer is 1 nm-1 mm.

4. The catalytic reactor according to claim 1 , wherein the catalytically active component is selected from the group consisting of metallic elements, nonmetallic elements, and combinations thereof.

5. The catalytic reactor according to claim 4 , wherein the metallic elements comprise: lithium, magnesium, aluminum, calcium, strontium, barium, titanium, manganese, vanadium, chromium, iron, cobalt, nickel, zinc, germanium, tin, gallium, zirconium, gold, lanthanum, cerium, praseodymium, neodymium, europium, erbium, and ytterbium.

6. The catalytic reactor according to claim 4 , wherein the nonmetallic elements comprise: boron and phosphorus.

7. A preparation method for a reaction section in a catalytic reactor, through a modified chemical vapor deposition (MCVD) method which is one of the following three methods:
the first method: at 1-3 atmospheric pressure, bringing silicon tetrachloride liquid under the drive of support gas or bringing the silicon tetrachloride liquid and nonmetallic chloride which is gas-phase doped at 50-500° C. under the drive of the support gas to enter an MCVD apparatus to react with oxygen at 1400-1650° C.; conducting vapor deposition of silicon-based thin layer with a thickness of 0.01-100 micrometers on the inner wall of the reaction section; subsequently immersing the reaction section at 20-80° C. into metal salt doped aqueous solution for 0.1-20 hours; then melting the immersed reaction section at 1800-2200° C. to obtain the corresponding metal lattice doped reaction section; forming a dopant thin layer with a thickness of 1 nm-1 mm on the inner wall of the reaction section; then immediately cooling; and curing to obtain the reaction section with catalytic activity;
the second method: at 1-3 atmospheric pressure, bringing silicon tetrachloride liquid and gas-phase-doped volatile metal salt which is gasified at 50-950° C. under the drive of support gas or bringing the silicon tetrachloride liquid, the gas-phase-doped volatile metal salt which is gasified at 50-950° C. and nonmetallic chloride which is gas-phase doped at 50-500° C. under the drive of the support gas to enter an MCVD apparatus to react with oxygen at 1400-1650° C.; conducting vapor deposition on the inner wall of the reaction section for 10 min-2 hour; subsequently melting at 1800-2200° C. to obtain the corresponding metal lattice doped reaction section; forming a dopant thin layer with a thickness of 1 nm-1 mm on the inner wall of the reaction section; then immediately cooling; and curing to obtain the reaction section with catalytic activity;
the third method: at 1-3 atmospheric pressure, bringing silicon tetrachloride liquid and normal-temperature liquid metal chloride or normal-temperature liquid nonmetallic chloride or oxygen chloride under the drive of support to enter an MCVD apparatus to react with oxygen at 1400-1650° C.; conducting vapor deposition on the inner wall of the reaction section for 10 min-2 hour; subsequently melting at 1800-2200° C. to obtain the corresponding metal lattice doped reaction section; forming a dopant thin layer with a thickness of 1 nm-1 mm on the inner wall of the reaction section; then immediately cooling; and curing to obtain the reaction section with catalytic activity.

8. A preparation method for a reaction section in a catalytic reactor, wherein the reactor adopts sol gel combined with a melting technology, the reaction section comprises an inner wall, and the method comprises: at room temperature, etching the inner wall of the reaction section for 1-48 hours using HF or NaOH solution, or grinding the inner wall of the reaction section is ground for 0.5-4 h using silicon-based particles of 40-100 meshes; preparing a mixed solution of metal salt, silicate and water; covering the mixed solution uniformly on the inner wall of the etched reaction section; conducting sol-gel reaction at 20-120° C. for 0.2-96 h; melting at 1800-2200° C. to obtain a corresponding metal lattice doped reaction section inner wall; then conducting immediate cooling; and curing to obtain the reactor with catalytic function.

9. The preparation method according to claim 7 , wherein the metal salt in the first method is at least one of nitrate, soluble halogenide, soluble sulphate, soluble carbonate, soluble calcium phosphate, soluble organic alkoxide with C number of 1-2, and organic acid salt with C number of 1-2.

10. The preparation method according to claim 7 , wherein the metal salt in the second method is at least one of metal chloride, organic alkoxide of C number of 1-2, and organic acid salt of C number of 1-2.

11. The preparation method according to claim 7 , wherein the normal-temperature liquid metal chloride in the third method is at least one of tin tetrachloride, titanium tetrachloride and germanium tetrachloride; and the normal-temperature liquid nonmetallic chloride or oxygen chloride is at least one of boron trichloride and phosphorous oxychloride.

12. The preparation method according to claim 8 , wherein the silicate is at least one of tetramethyl orthosilicate, tetraethoxysilane, tetrapropyl orthosilicate, isopropyl silicate, tetrabutyl orthosilicate and trimethylsiloxysilicate.

13. The preparation method according to claim 8 , wherein the content ratio of the metal salt to the silicate is 1:1000 to 1:1, and the content ratio of the silicate to water is 1:0.1 to 1:10.

14. The preparation method according to claim 8 , wherein in the sol-gel reaction process, the mass concentration of the metallic elements in the mixed solution of the metal salt, the silicate and the water is 50 ppm-10%; the treatment time of sol is 2-100 h; gel temperature is 10-120° C. and the treatment time of gel is 1-48 h.

15. The preparation method according to claim 8 , wherein the preparation process of the first method comprises an immersing process, and the solubility of immersion liquid is 50 ppm-5%; immersion time is 0.1-24 h; and immersion temperature is 20-80° C.

16. The preparation method according to claim 7 , wherein the thickness of the dopant thin layer is 1 nm-0.5 mm.

17. The preparation method according to claim 7 , wherein in the preparation process of the catalyst, deposition time is 10 min-1 h.

18. The preparation method according to claim 7 , wherein the flow velocity of the support gas is 5-2000 ml/min.

19. The preparation method according to claim 7 , wherein a melting atmosphere is at least one of inert gas, air, and oxygen; the inert gas comprises one or more of helium, argon or nitrogen; melting time is 0.01-3 h.

20. The preparation method according to claim 7 , wherein the cooling is gas cooling; a cooling rate is 50° C./s−2000° C./s; and the gas in the gas cooling is at least one of inert

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Bao Xinhe
• Guo Xiaoguang
• Fang Guangzong
• Pan Xiulian
• Meng Jingheng
• Yu Qinqin
• Tan Dali

Classifications

• B01J19/0013

  Controlling the temperature of the process · CPC title

• C23C16/402

  Silicon dioxide · CPC title

• C07C2521/08

  Silica · CPC title

• B01J2208/02

  with stationary particles · CPC title

• B01J2219/00835

  Comprising catalytically active material · CPC title