Catalytic reactor configuration, preparation and method of direct synthesis of ethylene through oxygen-free catalysis of methane
10661239 ยท 2020-05-26
Assignee
Inventors
- Xinhe Bao (Dalian, CN)
- Xiaoguang Guo (Dalian, CN)
- Guangzong Fang (Dalian, CN)
- Xiulian Pan (Dalian, CN)
- Jingheng Meng (Dalian, CN)
- Qinqin Yu (Dalian, CN)
- Dali Tan (Dalian, CN)
Cpc classification
Y02P20/52
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J2219/0093
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00835
PERFORMING OPERATIONS; TRANSPORTING
B01J15/00
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00159
PERFORMING OPERATIONS; TRANSPORTING
B01J12/007
PERFORMING OPERATIONS; TRANSPORTING
B01J10/007
PERFORMING OPERATIONS; TRANSPORTING
B01J19/0013
PERFORMING OPERATIONS; TRANSPORTING
C07C2/76
CHEMISTRY; METALLURGY
B01J19/02
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
B01J15/00
PERFORMING OPERATIONS; TRANSPORTING
B01J12/00
PERFORMING OPERATIONS; TRANSPORTING
B01J19/02
PERFORMING OPERATIONS; TRANSPORTING
B01J10/00
PERFORMING OPERATIONS; TRANSPORTING
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
C07C2/76
CHEMISTRY; METALLURGY
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.
Claims
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./s2000 C./s; and the gas in the gas cooling is at least one of inert gases, nitrogen, oxygen, and air.
21. The preparation method according to claim 7, wherein the support gas is high purity oxygen with a volume concentration above 99.9999% or high purity helium with a volume concentration above 99.9999%.
22. The preparation method according to claim 7, wherein the catalyst layer on the inner wall of the reactor only comprises lattice doped metallic elements and supports no metal or metal compound on the surface.
23. A method of direct synthesis of ethylene through oxygen-free catalysis of methane comprising catalyzing and converting methane in a feed gas to ethylene in the catalytic reactor of claim 1.
24. The method of direct synthesis of ethylene through oxygen-free catalysis of methane according to claim 23, wherein the temperature of the catalytic reaction is 750-1200 C.
25. The method of direct synthesis of ethylene through oxygen-free catalysis of methane according to claim 23 further comprising, before conducting the reaction, a pretreatment process in a pretreatment atmosphere that is at least one of reaction feed gas, hydrogen or air at a temperature of 750-900 C., a pretreatment pressure of 0.1-1 Mpa, and a weight hourly space velocity of the reaction feed gas of 0.8-2.5 L/g/h.
26. The method of direct synthesis of ethylene through oxygen-free catalysis of methane according to claim 23, wherein the feed gas is methane gas or a gas mixture of methane and other gases; besides methane, the reaction feed gas comprises optionally one or two of other inert gases and non-inert gases; the inert gases comprise at least one of nitrogen, helium, neon, argon and krypton, and the volume content of inert gas in the reaction feed gas is 0-95%; the non-inert gases comprise at least one of carbon monoxide, hydrogen, carbon dioxide, water, and alkanes with 2 to 4 carbon atoms, and the volume ratio of non-inert gas to methane is 0-10%; and the volume content of methane in the reaction feed gas is 5-100%.
27. The method of direct synthesis of ethylene through oxygen-free catalysis of methane according to claim 23, wherein the step of catalyzing and converting methane is conducted at a pressure of 0.05-1 MPa; and a weight hourly space velocity of the reaction feed gas of 1.0-30.0 L/g/h.
28. The method of direct synthesis of ethylene through oxygen-free catalysis of methane according to claim 23, wherein the step of catalyzing and converting methane also produces byproduct comprising at least one of propylene, butylene, aromatic hydrocarbon, and hydrogen, and wherein the aromatic hydrocarbon comprises at least one of benzene, toluene, xylene, o-xylene, m-xylene, ethylbenzene, and naphthalene.
29. The catalytic reactor according to claim 1 further comprising at least one of the following sections: an inlet section located at the front of the preheating section, a transition section located between the preheating section and the reaction section, and an outlet section located at the rear of the reaction section.
30. The catalytic reactor according to claim 29 comprising each of the inlet section, preheating section, the transition section, the reaction section, and the outlet section, wherein the inner diameter A of the inlet section, the inner diameter B of the preheating section, the inner diameter C of the transition section, the inner diameter D of the reaction section, and the inner diameter E of the outlet section are respectively 3-500 mm.
31. The catalytic reactor configuration according to claim 29 comprising each of the inlet section, the transition section, and outlet section, wherein none of the length I of the inlet section, the length III of the transition section, and the length V of the outlet section is larger than 5000 mm, and 0<I+III+V<5000 mm.
32. The catalytic reactor configuration according to claim 29 comprising each of the inlet section, preheating section, the transition section, the reaction section, and the outlet section, wherein the length I of the inlet section, the length II of the preheating section, the length III of the transition section, the length IV of the reaction section, and the length V of the outlet section satisfy: 0.1 m<I+II+III+IV+V<10 m.
33. The catalytic reactor configuration according to claim 30, wherein the inner diameter of each section needs to satisfy: D>A=B=C=E, or D=B>A=C=E, or B>D>A=C=E, or D>B>A=C=E, or A=B>D>C=E, or A=B>D>C>E, or A=B=C=D=E, or A=E>B=C=D, or A=C=E>B=D.
Description
DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
DESCRIPTION OF PREFERRED EMBODIMENTS
(4) The present invention is described below in details in combination with the drawings and the specific embodiments. However, the following embodiments are limited to explaining the present invention. The protection scope of the present invention should include all contents of claims, not limited to the embodiments.
(5) As shown in
(6) 1. Preparation of Reaction Section of Catalytic Reactor
(7) The preparation methods of the lattice doped catalyst include a modified chemical vapor deposition (MCVD) coated solid phase doping technology or a solid-liquid phase sol-gel combined high temperature melting and coating technology. The catalyst of the film is marked as ASiO.sub.xC.sub.y.
(8) The preparation of ASiO.sub.2 lattice doped catalysts (embodiments 1-20); the preparation of ASiC lattice doped catalysts (embodiments 21-26); the preparation of ASiOC.sub.0.5 all lattice doped catalysts (embodiments 27-30); the preparation of A/SiO.sub.2 support type catalysts (embodiment 31) (Active components are dispersed on the support surface); the preparation of A@SiO.sub.2 partial lattice doped catalysts (embodiments 32-34) (Active components are partially dispersed on the support surface, and a part of lattice is doped in the support, such as patent 201310174960.5).
Embodiment 1
(9) Modified Chemical Vapor Deposition (MCVD)
(10) SiCl.sub.4 liquid and FeCl.sub.3 gas of 350 C. are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1600 C., SiCl.sub.4 and FeCl.sub.3 conduct oxidation deposition on the inner wall of a quartz tube (with a wall thickness of 1.5 mm) with an outer diameter of 20 mm and a length of 100 mm for 10 minutes to obtain Fe doped SiO.sub.2 powder material; subsequently, under a temperature of 1980 C. and 2 bars of highly pure helium atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 50 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section A of a Fe catalytic quartz reactor with a diameter of 20 mm and a length of 100 mm, wherein the doping amount of Fe is 0.35 wt. %.
Embodiment 2
(11) Modified Chemical Vapor Deposition (MCVD)
(12) SiCl.sub.4 liquid and FeCl.sub.3 gas of 350 C. are brought into high temperature MCVD by using 30 mL/min of high purity helium; at 1650 C., SiCl.sub.4 and FeCl.sub.3 conduct high purity oxygen reaction on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 150 mm for oxidization deposition for 30 minutes to obtain Fe doped SiO.sub.2 powder material; subsequently, under a temperature of 1980 C. and 2 bars of highly pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 50 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section B of a Fe catalytic quartz reactor with a diameter of 20 mm and a length of 150 mm, wherein the doping amount of Fe is 0.6 wt. %.
Embodiment 3
(13) Modified Chemical Vapor Deposition (MCVD)
(14) SiCl.sub.4 liquid and ZnCl.sub.2 gas of 750 C. are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1600 C., SiCl.sub.4 and ZnCl.sub.2 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 200 mm for 30 minutes to obtain Zn doped SiO.sub.2 powder material; subsequently, under a temperature of 2000 C. and 1.5 bars of highly pure helium atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 50 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section C of a Zn catalytic quartz reactor with a diameter of 20 mm and a length of 200 mm, wherein the doping amount of Zn is 0.55 wt. %.
Embodiment 4
(15) Modified Chemical Vapor Deposition (MCVD)
(16) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., and ZnCl.sub.2 gas of 750 C. are brought into high temperature MCVD by using 30 mL/min of high purity helium; at 1600 C., SiCl.sub.4, FeCl.sub.3, and ZnCl.sub.2 react with highly pure oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 280 mm for 30 minutes to obtain SiO.sub.2 powder material doped with Fe and Zn; subsequently, under a temperature of 2000 C. and 1.5 bars of highly pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 100 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section D of a FeZnP catalytic quartz reactor with a diameter of 20 mm and a length of 280 mm, wherein the doping amounts of Fe and Zn are respectively 0.6 wt. % and 0.55 wt. %.
Embodiment 5
(17) Modified Chemical Vapor Deposition (MCVD)
(18) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., and ZnCl.sub.2 gas of 750 C. are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1600 C., SiCl.sub.4, FeCl.sub.3, and ZnCl.sub.2 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 50 mm (with a wall thickness of 2 mm) and a length of 350 mm for 60 minutes to obtain SiO.sub.2 powder material doped with Fe and Zn; subsequently, under a temperature of 2000 C. and 1.5 bars of highly pure argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 100 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section E of a FeZn catalytic quartz reactor with a diameter of 50 mm and a length of 350 mm, wherein the doping amounts of Fe and Zn are respectively 0.8 wt. % and 0.65 wt. %.
Embodiment 6
(19) Modified Chemical Vapor Deposition (MCVD)
(20) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1600 C., SiCl.sub.4, FeCl.sub.3, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 300 mm for 45 minutes to obtain SiO.sub.2 powder material doped with Fe, Zn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 80 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section F of a FeZnP catalytic quartz reactor with a diameter of 20 mm and a length of 300 mm, wherein the doping amounts of Fe, Zn and P are respectively 0.7 wt. %, 0.6 wt. % and 0.8 wt. %.
Embodiment 7
(21) Modified Chemical Vapor Deposition (MCVD)
(22) SiCl.sub.4 liquid, SnCl.sub.4 liquid, ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1600 C., SiCl.sub.4, SnCl.sub.4, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 250 mm for 45 minutes to obtain SiO.sub.2 powder material doped with Sn, Zn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 80 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section G of a FeZnP catalytic quartz reactor with a diameter of 20 mm and a length of 250 mm, wherein the doping amounts of Sn, Zn and P are respectively 0.4 wt. %, 0.6 wt. % and 0.8 wt. %.
Embodiment 8
(23) Modified Chemical Vapor Deposition (MCVD)
(24) SiCl.sub.4 liquid, SnCl.sub.4 liquid, ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity helium; at 1600 C., SiCl.sub.4, SnCl.sub.4, ZnCl.sub.2 and POCl.sub.3 react with the high purity oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 150 mm for 45 minutes to obtain SiO.sub.2 powder material doped with Sn, Zn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of high purity oxygen atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 85 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section H of a SnZnP catalytic quartz reactor with a diameter of 20 mm and a length of 150 mm, wherein the doping amounts of Sn, Zn and P are respectively 0.4 wt. %, 0.6 wt. % and 0.8 wt. %.
Embodiment 9
(25) Modified Chemical Vapor Deposition (MCVD)
(26) SiCl.sub.4 liquid, TiCl.sub.4 liquid, FeCl.sub.3 gas of 320 C. and BCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1600 C., SiCl.sub.4, TiCl.sub.4, FeCl.sub.3 and BCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 600 mm for 45 minutes to obtain SiO.sub.2 powder material doped with Ti, Fe and B; subsequently, under a temperature of 2000 C. and 1.5 bars of pure helium atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 40 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section I of a TiFeB catalytic quartz reactor with a diameter of 20 mm and a length of 600 mm, wherein the doping amounts of Ti, Fe and B are respectively 0.5 wt. %, 0.4 wt. % and 0.6 wt. %.
Embodiment 10
(27) Modified Chemical Vapor Deposition (MCVD)
(28) SiCl.sub.4 liquid, GaCl.sub.3 liquid of 220 C., and AlCl.sub.3 gas of 180 C. are brought into high temperature MCVD by using 30 mL/min of high purity helium; at 1650 C., SiCl.sub.4, GaCl.sub.3, and AlCl.sub.3 react with highly pure oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 250 mm for 40 minutes to obtain SiO.sub.2 powder material doped with Ga and Al; subsequently, under a temperature of 2000 C. and 1.5 bars of highly pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 60 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section J of a GaAl catalytic quartz reactor with a diameter of 20 mm and a length of 250 mm, wherein the doping amounts of Ga and Al are respectively 0.5 wt. % and 0.6 wt. %.
Embodiment 11
(29) Modified Chemical Vapor Deposition (MCVD)
(30) SiCl.sub.4 liquid, YbCl.sub.3 liquid of 900 C., AlCl.sub.3 gas of 180 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity helium; at 1650 C., SiCl.sub.4, YbCl.sub.3, POCl.sub.3 and AlCl.sub.3 react with highly pure oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 100 mm for 40 minutes to obtain SiO.sub.2 powder material doped with Yb and Al; subsequently, under a temperature of 2000 C. and 1.5 bars of high purity oxygen atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 80 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section K of a YbAlP catalytic quartz reactor with a diameter of 20 mm and a length of 100 mm, wherein the doping amounts of Yb, Al and P are respectively 0.2 wt. %, 0.5 wt. % and 0.6 wt. %.
Embodiment 12
(31) Modified Chemical Vapor Deposition (MCVD)
(32) SiCl.sub.4 liquid, LaCl.sub.3 liquid of 900 C., AlCl.sub.3 gas of 180 C. and BCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, LaCl.sub.3, BCl.sub.3 and AlCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 50 mm (with a wall thickness of 2 mm) and a length of 1500 mm for 80 minutes to obtain SiO.sub.2 powder material doped with La, Al and B; subsequently, under a temperature of 2000 C. and 1.5 bars of high purity helium atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 150 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section L of a LaAlB catalytic quartz reactor with a diameter of 50 mm and a length of 1500 mm, wherein the doping amounts of La, Al and B are respectively 0.2 wt. %, 0.4 wt. % and 0.6 wt. %.
Embodiment 13
(33) Modified Chemical Vapor Deposition (MCVD)
(34) SiCl.sub.4 liquid, LaCl.sub.3 liquid of 900 C., AlCl.sub.3 gas of 180 C. and BCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity helium; at 1650 C., SiCl.sub.4, LaCl.sub.3, BCl.sub.3 and AlCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 50 mm (with a wall thickness of 2 mm) and a length of 1200 mm for 80 minutes to obtain SiO.sub.2 powder material doped with La, Al and B; subsequently, under a temperature of 2000 C. and 1.5 bars of high purity argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 150 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section M of a LaAlB catalytic quartz reactor with a diameter of 50 mm and a length of 1200 mm, wherein the doping amounts of La, Al and B are respectively 0.2 wt. %, 0.4 wt. % and 0.6 wt. %.
Embodiment 14
(35) Modified Chemical Vapor Deposition (MCVD)
(36) SiCl.sub.4 liquid, BCl.sub.3 liquid, and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, BCl.sub.3, and POCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 25 mm (with a wall thickness of 1.5 mm) and a length of 250 mm for 30 minutes to obtain SiO.sub.2 powder material doped with B and P; subsequently, under a temperature of 2000 C. and 1.5 bars of highly pure helium atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 50 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section N of a PB catalytic quartz reactor with a diameter of 25 mm and a length of 250 mm, wherein the doping amounts of P and B are respectively 0.6 wt. % and 0.5 wt. %.
Embodiment 15
(37) Modified Chemical Vapor Deposition (MCVD)
(38) SiCl.sub.4 liquid, MgCl.sub.2 liquid of 950 C., MnCl.sub.2 liquid of 950 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, MgCl.sub.2, MnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 30 mm (with a wall thickness of 1.5 mm) and a length of 200 mm for 40 minutes to obtain SiO.sub.2 powder material doped with Mg, Mn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of highly pure helium atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 70 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section 0 of a MgMnP catalytic quartz reactor with a diameter of 30 mm and a length of 200 mm, wherein the doping amounts of Mg, Mn and P are respectively 0.6 wt. %, 0.5 wt. % and 0.7 wt. %.
Embodiment 16
(39) Modified Chemical Vapor Deposition (MCVD)
(40) SiCl.sub.4 liquid, MgCl.sub.2 liquid of 950 C., MnCl.sub.2 liquid of 950 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, MgCl.sub.2, MnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 30 mm (with a wall thickness of 1.5 mm) and a length of 900 mm for 40 minutes to obtain SiO.sub.2 powder material doped with Mg, Mn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of pure oxygen atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 70 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section P of a MgMnP catalytic quartz reactor with a diameter of 30 mm and a length of 900 mm, wherein the doping amounts of Mg, Mn and P are respectively 0.4 wt. %, 0.3 wt. % and 0.4 wt. %.
Embodiment 17
(41) Modified Chemical Vapor Deposition (MCVD)
(42) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., MnCl.sub.2 liquid of 950 C., POCl.sub.3 liquid, AlCl.sub.3 gas of 180 C. and SnCl.sub.4 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, FeCl.sub.3, MnCl.sub.2, AlCl.sub.3, SnCl.sub.4 and POCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 800 mm for 60 minutes to obtain SiO.sub.2 powder material doped with Fe, Mn, Sn, Al and P; subsequently, under a temperature of 2050 C. and 1.5 bars of pure oxygen atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 100 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section Q of a FeMnSnAlP catalytic reactor with a diameter of 20 mm and a length of 800 mm, wherein the doping amounts of Fe, Mn, Sn, Al and P are respectively 0.4 wt. %, 0.3 wt. %, 0.2 wt. %, 0.45 wt. % and 0.4 wt. %.
Embodiment 18
(43) Modified Chemical Vapor Deposition (MCVD)
(44) SiCl.sub.4 liquid is brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4 conducts oxidation deposition on the inner wall of a quartz tube with an outer diameter of 20 mm (with a wall thickness of 1.5 mm) and a length of 500 mm for 40 minutes to obtain SiO.sub.2 powder material; subsequently, under a temperature of 50 C., the quartz tube of 20 mm is immersed in an aqueous solution of SrCl.sub.2 and Ba(NO.sub.3).sub.2 to for about 2 h; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 300 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section R of a SrBa catalytic quartz reactor with a diameter of 20 mm and a length of 500 mm, wherein the doping amounts of Sr and Ba are respectively 0.4 wt. % and 0.4 wt. %.
Embodiment 19
(45) Modified Chemical Vapor Deposition (MCVD)
(46) SiCl.sub.4 liquid, LaCl.sub.3 liquid of 900 C., AlCl.sub.3 gas of 180 C. and BCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, LaCl.sub.3, BCl.sub.3 and AlCl.sub.3 conduct oxidation deposition on the inner wall of a quartz tube with an outer diameter of 50 mm (with a wall thickness of 2 mm) and a length of 200 mm for 80 minutes to obtain SiO.sub.2 powder material doped with La, Al and B; subsequently, under a temperature of 50 C., the quartz reactor of 50 mm is immersed in an aqueous solution of AuCl.sub.3 to for about 1 h; subsequently, under a temperature of 2000 C. and 1.5 bars of pure oxygen atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 100 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section S of a LaAlAuB catalytic quartz reactor with a diameter of 50 mm and a length of 200 mm, wherein the doping amounts of La, Al, Au and B are respectively 0.4 wt. %, 0.5 wt. %, 0.1 wt. % and 0.4 wt. %.
Embodiment 20
(47) Modified Chemical Vapor Deposition (MCVD)
(48) SiCl.sub.4 liquid, LaCl.sub.3 liquid of 900 C., AlCl.sub.3 gas of 180 C. and BCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, LaCl.sub.3, BCl.sub.3 and AlCl.sub.3 conduct oxidation deposition on the inner wall of a quartz tube with an outer diameter of 50 mm (with a wall thickness of 2 mm) and a length of 300 mm for 80 minutes to obtain SiO.sub.2 powder material doped with La, Al and B; subsequently, under a temperature of 50 C., the quartz reactor of 50 mm is immersed in an aqueous solution of AuCl.sub.3 to for about 1 h; subsequently, under a temperature of 2000 C. and 1.5 bars of pure oxygen atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 80 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section T of a LaAlAuB catalytic quartz reactor with a diameter of 50 mm and a length of 300 mm, wherein the doping amounts of La, Al, Au and B are respectively 0.3 wt. %, 0.5 wt. %, 0.2 wt. % and 0.5 wt. %.
Embodiment 21
(49) Modified Chemical Vapor Deposition (MCVD)
(50) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, FeCl.sub.3, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of 40 mm (with a wall thickness of 2 mm) and a length of 300 mm for 60 minutes to obtain SiO.sub.2 powder material doped with Fe, Zn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 80 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section U of a FeZnP catalytic quartz reactor with a diameter of 40 mm and a length of 300 mm, wherein the doping amounts of Fe, Zn and P are respectively 0.6 wt. %, 0.5 wt. % and 0.35 wt. %.
Embodiment 22
(51) Modified Chemical Vapor Deposition (MCVD)
(52) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, FeCl.sub.3, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of 20 mm (with a wall thickness of 2.5 mm) and a length of 400 mm for 60 minutes to obtain SiO.sub.2 powder material doped with Fe, Zn and P; subsequently, under a temperature of 1650 C., CH.sub.4 is led to conduct carbonizing treatment for 60 minutes; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 120 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section V of a FeZnP catalytic silica carbide reactor with a diameter of 20 mm and a length of 400 mm, wherein the doping amounts of Fe, Zn and P are respectively 0.2 wt. %, 0.3 wt. % and 0.5 wt. %.
Embodiment 23
(53) Modified Chemical Vapor Deposition (MCVD)
(54) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, FeCl.sub.3, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of 20 mm (with a wall thickness of 2.5 mm) and a length of 600 mm for 60 minutes to obtain SiO.sub.2 powder material doped with Fe, Zn and P; subsequently, under a temperature of 1650 C., CH.sub.4 is led at 60 ml/min to conduct carbonizing treatment for 60 minutes; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 800 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section W of a FeZnP catalytic silica carbide reactor with a diameter of 20 mm and a length of 600 mm, wherein the doping amounts of Fe, Zn and P are respectively 0.3 wt. %, 0.2 wt. % and 0.4 wt. %.
Embodiment 24
(55) Modified Chemical Vapor Deposition (MCVD)
(56) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, FeCl.sub.3, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of 20 mm (with a wall thickness of 2.5 mm) and a length of 360 mm for 80 minutes to obtain SiO.sub.2 powder material doped with Fe, Zn and P; subsequently, under a temperature of 1650 C., CH.sub.4 is led at 40 ml/min to conduct carbonizing treatment for 60 minutes; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 600 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section X of a FeZnP catalytic silica carbide reactor with a diameter of 50 mm and a length of 360 mm, wherein the doping amounts of Fe, Zn and P are respectively 0.4 wt. %, 0.3 wt. % and 0.2 wt. %.
Embodiment 25
(57) Modified Chemical Vapor Deposition (MCVD)
(58) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, FeCl.sub.3, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of 20 mm (with a wall thickness of 2 mm) and a length of 600 mm for 40 minutes to obtain SiO.sub.2 powder material doped with Fe, Zn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 500 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the SiO.sub.2 coated reaction section Y of a FeZnP catalytic silica carbide reactor with a diameter of 20 mm and a length of 600 mm, wherein the doping amounts of Fe, Zn and P are respectively 0.3 wt. %, 0.2 wt. % and 0.2 wt. %.
Embodiment 26
(59) Modified Chemical Vapor Deposition (MCVD)
(60) SiCl.sub.4 liquid, FeCl.sub.3 gas of 350 C., ZnCl.sub.2 gas of 750 C. and POCl.sub.3 liquid are brought into high temperature MCVD by using 30 mL/min of high purity oxygen; at 1650 C., SiCl.sub.4, FeCl.sub.3, ZnCl.sub.2 and POCl.sub.3 conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of 50 mm (with a wall thickness of 3 mm) and a length of 400 mm for 80 minutes to obtain SiO.sub.2 powder material doped with Fe, Zn and P; subsequently, under a temperature of 2000 C. and 1.5 bars of pure argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 300 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the SiO.sub.2 coated reaction section Z of a FeZnP catalytic silica carbide reactor with a diameter of 50 mm and a length of 400 mm, wherein the doping amounts of Fe, Zn and P are respectively 0.1 wt. %, 0.4 wt. % and 0.35 wt. %.
Embodiment 27
(61) A sol-gel method is combined with a high temperature melting technology.
(62) The inner wall of the quartz tube with an outer diameter of 13 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.3688 g of Fe(NO.sub.3).sub.3.9H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2050 C. and normal pressure air atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 90 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AA of a Fe catalytic quartz reactor with a diameter of 13 mm and a length of 100 mm, wherein the doping amount of Fe is 0.5 wt. %.
Embodiment 28
(63) A sol-gel method is combined with a high temperature melting technology.
(64) The inner wall of the quartz tube with an outer diameter of 16 mm and a length of 400 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.5344 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 6 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 1950 C. and normal pressure air atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 120 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AB of a Mg catalytic quartz reactor with a diameter of 16 mm and a length of 400 mm, wherein the doping amount of Mg is 0.6 wt. %.
Embodiment 29
(65) A sol-gel method is combined with a high temperature melting technology.
(66) The inner wall of the quartz tube with an outer diameter of 20 mm and a length of 200 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.2288 g of Zn(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2000 C. and normal pressure air atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 200 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AC of a Zn catalytic quartz reactor with a diameter of 20 mm and a length of 200 mm, wherein the doping amount of Zn is 0.5 wt. %.
Embodiment 30
(67) A sol-gel method is combined with a high temperature melting technology.
(68) The inner wall of the quartz tube with an outer diameter of 20 mm and a length of 250 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.1559 of La(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2000 C. and normal pressure air atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 150 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AD of a La catalytic quartz reactor with a diameter of 20 mm and a length of 250 mm, wherein the doping amount of La is 0.6 wt. %.
Embodiment 31
(69) A sol-gel method is combined with a high temperature melting technology.
(70) The inner wall of the quartz tube with an outer diameter of 13 mm and a length of 220 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.1555 g of Ce(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2000 C. and 1.1 bars of pure oxygen atmosphere, the material is melted for 30 minutes; then, a dopant thin layer with a thickness of 180 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AE of a Ce catalytic quartz reactor with a diameter of 13 mm and a length of 220 mm, wherein the doping amount of Ce is 0.5 wt. %.
Embodiment 32
(71) A sol-gel method is combined with a high temperature melting technology.
(72) The inner wall of the quartz tube with an outer diameter of 25 mm and a length of 200 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.082 g of Ga(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2100 C. and 1.1 bars of pure oxygen atmosphere, the material is melted for 40 minutes; then, a dopant thin layer with a thickness of 180 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AF of a Ga catalytic quartz reactor with a diameter of 25 mm and a length of 200 mm, wherein the doping amount of Ga is 0.4 wt. %.
Embodiment 33
(73) A sol-gel method is combined with a high temperature melting technology.
(74) The inner wall of the quartz tube with an outer diameter of 30 mm and a length of 170 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.5344 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 0.3688 g of Fe(NO.sub.3).sub.3.9H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2050 C. and 1.2 bars of air atmosphere, the material is melted for 50 minutes; then, a dopant thin layer with a thickness of 180 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AG of a FeMg catalytic quartz reactor with a diameter of 30 mm and a length of 170 mm, wherein the doping amounts of Fe and Mg are 0.4 wt. % and 0.6 wt. %.
Embodiment 34
(75) A sol-gel method is combined with a high temperature melting technology.
(76) The inner wall of the quartz tube with an outer diameter of 25 mm is treated for 2 h by using 20% of HF solution; meanwhile, a mixed solution of 0.5344 g and 0.3688 g of Fe(NO.sub.3).sub.3.9H.sub.2O, 0.1559 g of La(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2050 C. and normal pressure air atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 220 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AH of a Mg catalytic quartz reactor with a diameter of 25 mm and a length of 200 mm, wherein the doping amount of Mg is 0.3 wt. %.
Embodiment 35
(77) A sol-gel method is combined with a high temperature melting technology.
(78) The inner wall of the quartz tube with an outer diameter of 20 mm and a length of 200 mm is treated for 2 h by using 2M of NaOH solution; meanwhile, a mixed solution of 0.3688 g of Fe(NO.sub.3).sub.3.9H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2050 C. and normal pressure argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 100 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AI of a Fe catalytic quartz reactor with a diameter of 20 mm and a length of 200 mm, wherein the doping amount of Fe is 0.6 wt. %.
Embodiment 36
(79) A sol-gel method is combined with a high temperature melting technology.
(80) The inner wall of the quartz tube with an outer diameter of 16 mm and a length of 300 mm is treated for 2 h by using 2M of NaOH solution; meanwhile, a mixed solution of 0.5344 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2000 C. and normal pressure argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 1 micrometer is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AJ of a Mg catalytic quartz reactor with a diameter of 16 mm and a length of 300 mm, wherein the doping amount of Mg is 0.2 wt. %.
Embodiment 37
(81) A sol-gel method is combined with a high temperature melting technology.
(82) The inner wall of the quartz tube with an outer diameter of 13 mm and a length of 200 mm is treated for 2 h by using 2M of NaOH solution; meanwhile, a mixed solution of 0.2288 g of Zn(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2100 C. and 1.1 bars of argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 800 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AK of a Zn catalytic quartz reactor with a diameter of 13 mm and a length of 200 mm, wherein the doping amount of Zn is 0.45 wt. %.
Embodiment 38
(83) A sol-gel method is combined with a high temperature melting technology.
(84) The inner wall of the quartz tube with an outer diameter of 30 mm and a length of 300 mm is treated for 2 h by using 2M of NaOH solution; meanwhile, a mixed solution of 0.1559 g of La(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2100 C. and 1.2 bars of argon atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 500 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AL of a La catalytic quartz reactor with a diameter of 30 mm and a length of 300 mm, wherein the doping amount of La is 0.6 wt. %.
Embodiment 39
(85) A sol-gel method is combined with a high temperature melting technology.
(86) The inner wall of the quartz tube with an outer diameter of 10 mm and a length of 50 mm is treated for 2 h by using 2M of NaOH solution; meanwhile, a mixed solution of 0.1555 g of Ce(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2000 C. and 1.1 bars of argon atmosphere, the material is melted for 50 minutes; then, a dopant thin layer with a thickness of 600 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AM of a Ce catalytic quartz reactor with a diameter of 10 mm and a length of 50 mm, wherein the doping amount of Ce is 0.55 wt. %.
Embodiment 40
(87) A sol-gel method is combined with a high temperature melting technology.
(88) The inner wall of the quartz tube with an outer diameter of 17 mm and a length of 50 mm is treated for 2 h by using 2M of NaOH solution; meanwhile, a mixed solution of 0.082 g of Ga(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2000 C. and 1.1 bars of helium atmosphere, the material is melted for 50 minutes; then, a dopant thin layer with a thickness of 300 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AN of a Ga catalytic quartz reactor with a diameter of 17 mm and a length of 50 mm, wherein the doping amount of Ga is 0.35 wt. %.
Embodiment 41
(89) A sol-gel method is combined with a high temperature melting technology.
(90) The inner wall of the quartz tube with an outer diameter of 25 mm and a length of 330 mm is treated for 2 h by using 2M of NaOH solution; meanwhile, a mixed solution of 0.5344 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 0.3688 g of Fe(NO.sub.3).sub.3.9H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2100 C. and 1.1 bars of helium atmosphere, the material is melted for 50 minutes; then, a dopant thin layer with a thickness of 750 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AO of a FeMg catalytic quartz reactor with a diameter of 25 mm and a length of 330 mm, wherein the doping amounts of Fe and Mg are 0.35 wt. % and 0.45 wt. %.
Embodiment 42
(91) A sol-gel method is combined with a high temperature melting technology.
(92) The inner wall of the quartz tube with an outer diameter of 25 mm and a length of 330 mm is treated for 2 h by using superfine SiC particles with 80-100 meshes to coarsen the inner surface of the quartz tube; meanwhile, a mixed solution of 0.5344 g and 0.3688 g of Fe(NO.sub.3).sub.3.9H.sub.2O, 0.1559 g of La(NO.sub.3).sub.2.6H.sub.2O, 33 mL of tetraethoxysilane TEOS and 50 mL of deionized water is prepared; after uniformly stirred, 4 mL is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of 90 C. for 3 h; finally, under a temperature of 2000 C. and 1.2 bars of helium atmosphere, the material is melted for 60 minutes; then, a dopant thin layer with a thickness of 150 nm is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AP of a FeLa catalytic quartz reactor with a diameter of 25 mm and a length of 330 mm, wherein the doping amounts of Fe and La are 0.4 wt. % and 0.5 wt. %.
(93) 2. Characterization of Inner Wall of Reaction Section of Catalytic Reactor
(94) 1) Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) Characterization
(95) The ICP-AES acid leaching (nitric acid and HF acid) method is used. The so-called ICP-AES acid leaching process is that the metal on the surface of the support can be dissolved by an acid leaching process if the metal is loaded on the surface of the support (the acid can only dissolve the metal component, but the metal oxide component cannot dissolve the support); degree of acid leaching (i.e., a ratio of surface loadings to surface loading and doping amount) can be obtained through ICP measurement; however, if the metallic elements cannot be dissolved by acid, it indicates that the metallic elements are doped in the Si-based support lattice and protected. Firstly, the reaction section A of the Fecatalytic quartz reactor with a diameter of 20 mm is leached by dilute nitric acid, and the ICP analysis results show that no Fe ion is dissolved, and further indicate that all of Fe ions enter the lattice of Si-based substrate. However, if HF acid is adopted, not only the Si-based substrate can be dissolved, but also the metal components can be dissolved. The ICP analysis results show that all of Fe ions are dissolved, and the amount is just converted into the doping amount. The above analysis results show that all of Fe ions have been doped inside the lattice of Si-based substrate, and almost no Fe can be detected on the surface of Si-based substrate.
(96) 2) Characterization of HAADF-STEM High-Resolution Electron Microscope and EDX of Reaction Section A of Fe Catalytic Quartz Reactor with a Diameter of 20 mm
(97) A in
(98) 3. Under the Oxygen-Free and Continuous Flow Conditions, Methane is Directly Converted to Olefin, Aromatic Hydrocarbon and Hydrogen
(99) All of the above catalytic reactors are directly used without loading the catalysts.
(100) All of the reaction examples are achieved in a continuous flow micro-reaction apparatus, which is equipped with gas mass flow meters, gas deoxy and dehydration tubes, and online product analysis chromatography (The tail gas of the reactor is directly connected with the metering valve of chromatography, and periodic and real-time sampling and analysis will be achieved.). The reaction feed gas is composed of 10 vol. % N.sub.2 and 90 vol. % CH.sub.4 without specification, in which the nitrogen (N.sub.2) is used as internal standard gas. To achieve the online product analysis, the Agilent 7890A chromatography with dual detectors of FID and TCD is used, wherein the FID detector with HP-1 capillary column is used to analyze the light olefin, light alkane and aromatic hydrocarbon; and the TCD detector with Hayesep D packed column is used to analyze the light olefin, light alkane, methane, hydrogen and internal standard N.sub.2. According to the carbon balance before and after reaction, methane conversion, carbonic product selectivity and coke deposition are calculated by the method from the patents (CN1247103A and CN1532546A).
Embodiment 1
(101) The reaction section A (with a diameter of 20 mm and a length of 100 mm) (embodiment 1 for preparation of the reaction section of the catalytic reactor) of the Fe catalytic quartz reactor, the quartz preheating section (with a diameter of 8 mm and a length of 600 mm) and the quartz transition section (with a diameter of 14 mm and a length of 50 mm) are connected in accordance with
Embodiments 2-12
(102) The reaction section J (with a diameter of 20 mm and a length of 250 mm) (embodiment 10 for preparation of the reaction section of the catalytic reactor) of the GaAl catalytic quartz reactor, the quartz inlet section (with a diameter of 10 mm and a length of 100 mm), the quartz preheating section (with a diameter of 15 mm and a length of 300 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
(103) TABLE-US-00002 Hourly Methane Temper- Space Conversion Ethylene Propylene Butylene Benzene Naphthalene Embod- ature Velocity Rate Selectivity Selectivity Selectivity Selectivity Selectivity iments ( C.) (L/g/h) (%) (%) (%) (%) (%) (%) 2 750 1.6 4.2 77 6 0 15 2 3 850 2.2 6.3 75 8 0 14 3 4 900 3.6 10.2 73 8 0 15 4 5 950 4.8 19.5 73 5 6 16 0 6 960 6.0 21.3 72 8 4 15 1 7 970 7.2 24.5 70 7 0 18 5 8 980 8.4 26.8 70 6 6 15 3 9 990 9.6 29.2 68 8 5 18 1 10 1000 10.8 32.3 69 8 0 18 5 11 1010 12.0 37.5 66 9 0 20 5 12 1020 13.2 39.2 68 10 1 21 0
Embodiments 13-23
(104) The reaction section O (with a diameter of 30 mm and a length of 200 mm) (embodiment 15 for preparation of the reaction section of the catalytic reactor) of the MgMnP catalytic quartz reactor, the quartz preheating section (with a diameter of 15 mm and a length of 300 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
(105) TABLE-US-00003 Hourly Methane Temper- Space Conversion Ethylene Propylene Butylene Benzene Naphthalene Embod- ature Velocity Rate Selectivity Selectivity Selectivity Selectivity Selectivity iments ( C.) (L/g/h) (%) (%) (%) (%) (%) (%) 13 750 3.2 3.4 76 6.5 0 16 1.5 14 850 4.2 5.5 74 8.5 0 15 2.5 15 900 5.6 9.4 72 8.5 0 16 3.5 16 950 6.8 18.7 72 5.5 6 16.5 0 17 960 8.0 20.5 71 8.5 4 16 0.5 18 970 9.2 23.7 69 7.5 0 19 4.5 19 980 10.4 26 69 6.5 6 16 2.5 20 990 11.2 28.4 67 8.5 5 19 0.5 21 1000 13.8 31.5 68 8.5 0 19 4.5 22 1010 15.6 36.7 65 9.5 0 21 4.5 23 1020 18.2 38.4 67 10.5 1 21.5 0
Embodiments 24-34
(106) The reaction section L (with a diameter of 50 mm and a length of 1500 mm) (embodiment 12 for preparation of the reaction section of the catalytic reactor) of the LaAlB catalytic quartz reactor, the quartz preheating section (with a diameter of 15 mm and a length of 300 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
(107) TABLE-US-00004 Hourly Methane Temper- Space Conversion Ethylene Propylene Butylene Benzene Naphthalene Embod- ature Velocity Rate Selectivity Selectivity Selectivity Selectivity Selectivity iments ( C.) (L/g/h) (%) (%) (%) (%) (%) (%) 24 750 12 3.8 77.1 5.9 0 15 1.9 25 850 15 5.9 75.1 7.9 0 14 2.9 26 900 22 9.8 73.1 7.9 0 15 3.9 27 950 29 19.1 73.1 4.9 6 15.5 0.4 28 960 32 20.9 72.1 7.9 4 15 0.9 29 970 35 24.1 70.1 6.9 0 18 4.9 30 980 37 26.4 70.1 5.9 6 15 2.9 31 990 41 28.8 68.1 7.9 5 18 0.9 32 1000 42 31.9 69.1 7.9 0 18 4.9 33 1010 46 37.1 66.1 8.9 0 20 4.9 34 1020 50 38.8 68.1 9.9 1 20.5 0.4
Embodiment 35
(108) The reaction section P (with a diameter of 30 mm and a length of 900 mm) (embodiment 17 for preparation of the reaction section of the catalytic reactor) of the FeMnSnAlP catalytic quartz reactor, the quartz inlet section (with a diameter of 8 mm and a length of 100 mm), the quartz preheating section (with a diameter of 15 mm and a length of 300 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 200 mm) are connected in accordance with
(109) TABLE-US-00005 Methane Time Con- Ethylene Propylene Butylene Benzene Naphthalene inter- version Selec- Selec- Selec- Selec- Selec- val Rate tivity tivity tivity tivity tivity (hour) (%) (%) (%) (%) (%) (%) 100 47.9 70 8 0 16 6 200 48.5 69 10 0 18 3 300 49.0 67 9 0 18 8 400 49.8 68 8 1 20 3 500 49.5 66 8 2 20 4 600 40.3 65 7 0 23 5 700 49.2 67 9 0 20 4 800 48.5 65 8 0 22 5 900 51 68 9 0 20 3 1000 49.8 69 8 0 21 2
Embodiment 36
(110) The reaction section V (with a diameter of 30 mm and a length of 300 mm) (embodiment 21 for preparation of the reaction section of the catalytic reactor) of the FeZnP catalytic silica carbide reactor, the quartz inlet section (with a diameter of 8 mm and a length of 100 mm), the quartz preheating section (with a diameter of 15 mm and a length of 260 mm), the transition section (with a diameter of 15 mm and a length of 60 mm) and the outlet section (with a diameter of 6 mm and a length of 250 mm) are connected in accordance with
Embodiment 37
(111) The reaction section W (with a diameter of 50 mm and a length of 600 mm) (embodiment 23 for preparation of the reaction section of the catalytic reactor) of the FeZnP catalytic silica carbide reactor, the quartz inlet section (with a diameter of 8 mm and a length of 100 mm), the quartz preheating section (with a diameter of 15 mm and a length of 300 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 200 mm) are connected in accordance with
Embodiment 38
(112) The reaction section X (with a diameter of 20 mm and a length of 360 mm) (embodiment 24 for preparation of the reaction section of the catalytic reactor) of the FeZnP catalytic silica carbide reactor, the quartz inlet section (with a diameter of 8 mm and a length of 100 mm), the quartz preheating section (with a diameter of 15 mm and a length of 400 mm), the transition section (with a diameter of 15 mm and a length of 60 mm) and the outlet section (with a diameter of 6 mm and a length of 200 mm) are connected in accordance with
Embodiment 39
(113) The reaction section AA (with a diameter of 13 mm and a length of 100 mm) (embodiment 27 for preparation of the reaction section of the catalytic reactor) of the Fe catalytic quartz reactor, the quartz preheating section (with a diameter of 15 mm and a length of 600 mm), the transition section (with a diameter of 15 mm and a length of 60 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
Embodiment 40
(114) The reaction section AC (with a diameter of 20 mm and a length of 200 mm) (embodiment 29 for preparation of the reaction section of the catalytic reactor) of the Zn catalytic quartz reactor, the quartz inlet section (with a diameter of 15 mm and a length of 60 mm), the quartz preheating section (with a diameter of 20 mm and a length of 600 mm), the transition section (with a diameter of 15 mm and a length of 60 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with the figure to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of 30 ml/min for about 30 mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to 950 C. at a heating rate of 6 C./min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to 4.8 L/g/h. After the WHSV being kept for 30 mins, online analysis is started. The analysis results are as follows: 12.4% of methane conversion, 48.2% of ethylene selectivity, 6.0% of propylene and butylene selectivity and 22.0% of benzene selectivity. For the 0.5 wt. % ZnSiO.sub.2 catalyst prepared by the method from patents 201310174960.5 and 201511003407.0, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by 3%.
Embodiment 41
(115) The reaction section AD (with a diameter of 20 mm and a length of 250 mm) (embodiment 30 for preparation of the reaction section of the catalytic reactor) of the La catalytic quartz reactor, the quartz inlet section (with a diameter of 10 mm and a length of 60 mm), the quartz preheating section (with a diameter of 15 mm and a length of 600 mm), the transition section (with a diameter of 15 mm and a length of 60 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
Embodiment 42
(116) The reaction section AL (with a diameter of 30 mm and a length of 300 mm) (embodiment 38 for preparation of the reaction section of the catalytic reactor) of the La catalytic quartz reactor, the quartz inlet section (with a diameter of 14 mm and a length of 60 mm), the quartz preheating section (with a diameter of 20 mm and a length of 500 mm), the transition section (with a diameter of 15 mm and a length of 60 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
Embodiment 43
(117) The reaction section AL (with a diameter of 25 mm and a length of 330 mm) (embodiment 41 for preparation of the reaction section of the catalytic reactor) of the FeMg catalytic quartz reactor, the quartz inlet section (with a diameter of 14 mm and a length of 60 mm), the quartz preheating section (with a diameter of 20 mm and a length of 500 mm), the transition section (with a diameter of 15 mm and a length of 60 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
Embodiment 44
(118) The reaction section J (with a diameter of 20 mm and a length of 300 mm) (embodiment 6 for preparation of the reaction section of the catalytic reactor) of the FeZnP catalytic quartz reactor, the quartz inlet section (with a diameter of 10 mm and a length of 100 mm), the quartz preheating section (with a diameter of 20 mm and a length of 500 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
Embodiment 45
(119) The reaction section J (with a diameter of 20 mm and a length of 300 mm) (embodiment 6 for preparation of the reaction section of the catalytic reactor) of the FeZnP catalytic quartz reactor, the quartz inlet section (with a diameter of 10 mm and a length of 100 mm), the quartz preheating section (with a diameter of 20 mm and a length of 500 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with
Embodiment 46
(120) The reaction section J (with a diameter of 20 mm and a length of 300 mm) (embodiment 6 for preparation of the reaction section of the catalytic reactor) of the FeZnP catalytic quartz reactor, the quartz inlet section (with a diameter of 10 mm and a length of 100 mm), the quartz preheating section (with a diameter of 20 mm and a length of 500 mm), the transition section (with a diameter of 15 mm and a length of 50 mm) and the outlet section (with a diameter of 6 mm and a length of 100 mm) are connected in accordance with -0.6 wt. % Zn-0.8 wt. % PSiO.sub.2 catalyst prepared by the method from patents 201310174960.5 and 201511003407.0, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by 11%.
(121) In summary, under the pattern in the catalytic reactor of the present invention, reaction temperature is 750-1100 C.; reaction pressure is normal pressure; the weight hourly space velocity of methane is 1.0-30.0 L/g/h; methane conversion is 10-70%; ethylene selectivity is 60-95%; propylene and butylene selectivities are 5-25%; and aromatic hydrocarbon selectivity is 0-25%.
(122) It is concluded that the present invention has the characteristics of long catalyst life (>500 hrs) of the catalytic reactor, high stability of redox and hydrothermal properties under high temperature (<1400 C.), high product selectivity, zero coke deposition, easy separation of products, good process reproducibility, safe and reliable operation, etc., and has wide industrial application prospect.
(123) It should be noted that in accordance with the above embodiments of the present invention, those skilled in the art can completely realize the full scope of independent claims and dependent claims of the present invention; the realization processes and methods are the same as those of the above embodiments; and a part not described in detail in the present invention belongs to a widely-known technology in the field.
(124) The above is just part of concrete implementation manners of the present invention, but the protection scope of the present invention is not limited thereto. Any change or replacement contemplated easily by those skilled in the art familiar with the technical field within the technical scope disclosed by the present invention shall be covered within the protection scope of the present invention.