CN109847654A

CN109847654A - A kind of preparation of silicon carbide reactor device and its application in methane olefin process directly processed

Info

Publication number: CN109847654A
Application number: CN201711239884.6A
Authority: CN
Inventors: 包信和; 方光宗; 潘秀莲; 吕厚甫; 谭大力
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2017-11-30
Filing date: 2017-11-30
Publication date: 2019-06-07
Anticipated expiration: 2037-11-30
Also published as: CN109847654B

Abstract

Type of the present invention and a kind of silicon carbide reactor device, the material of the reactor is the silicon carbide of metallic element impurity, utilize the good thermal conductivity and chemical reaction inert nature of the material, based on the reactor direct synthesizing ethylene of catalytic methane under anaerobic, the nil product carbon and ethylene high selectivity of methane are realized, the conversion ratio of methane is 10~70%；Ethylene selectivity is 40~75%；Propylene Selectivity is 5~15%；Arenes selectivity is 0~40%；Nil product carbon.The present invention has the characteristics that good catalyst life long (>1000h), catalyst high temperature (<1700 DEG C) stability inferior, methane conversion and selectivity of product height, nil product carbon, industrialization difficulty is small, process is reproducible, safe operation is reliable, has wide prospects for commercial application.

Description

A kind of silicon carbide reactor device is prepared and its in methane olefin process directly processed Using

Technical field

The present invention relates to a kind of novel reactors based on silicon carbide material, and are successfully applied to methane direct conversion second Alkene, aromatic hydrocarbons and hydrogen process.The process realizes that methane Efficient Conversion, ethylene high selectivity and nil product carbon generate, and belongs to and urges Change reactor technology field.

Background technique

Natural gas is a kind of high-quality, clean energy, and main component is methane (CH4).The reserves of world's methane are very It is huge, the discovery of methane is especially hydrated in North America, Chinese shale gas and bottom sediment recently, so that the reserves of methane reach All 2 times (being calculated by phosphorus content) for verifying fossil energy.In recent years, the production and consumption sustainable growth of world's natural gas, Ratio in primary energy structure rises to current 24% via the 9.8% of nineteen fifty, and the year two thousand twenty is estimated to be up to 29%, One of the main energy sources of 21 century will be become.Compared with its yield, the consumption industry of natural gas is still immature, chemical industry natural gas Share it is also relatively low.With persistently raising up for crude oil price, the price of downstream chemical products (alkene, aromatic hydrocarbons) is caused to occupy height not Under.Therefore, how research carries out catalytic activation and effective use to methane, is one of the significant challenge faced at present in science, And be effectively relieved energy crisis and realize sustainable development there is an urgent need to.

Methane chemical utilization can be divided into two Basic Ways of indirect method and direct method.Methane indirect reformer method is being changed at present The utilization learned in Chemical Manufacture is relatively mature, and namely for methane passes through reforming reaction (steam reforming, CO 2 reformation first And partial oxidation) be made the synthesis gas of certain C/Hratio, then by synthesis gas through different approaches (such as Fischer-Tropsch Fischer-Tropsch, Synthesising gas systeming carbinol STO, synthesis gas gasoline STG, synthesis ammonia etc.) obtain a series of industrial chemicals and oil product.Due to switching through Chemical industry skill is cumbersome, high production cost, and a large amount of CO2 are especially generated in technical process, therefore, directly converts methane to high added value Chemical products be always focus concerned by people.

The direct conversion of methane is broadly divided into three processes: Catalyst for Oxidative Coupling of Methane (OCM), methane selective oxidation Methanol or formaldehyde (SOM) processed, methane non oxidative aromatization (MDA).Nineteen eighty-two U.S. UCC, the Keller and Bhasin of company were reported for the first time The road reaction of methane oxidation coupling C2 hydrocarbon (OCM), can achieve 14% methane conversion and 5% C2 at 1023K Thus hydrocarbon-selective opens a methane direct conversion and utilizes new way.So far, methane conversion up to 20%~ 40%, C2 selectivity up to 50%~80%, C2 hydro carbons yield up to 14%~25%, but in the case of facing oxygen due to high temperature, first Alkane deep oxidation generates a large amount of CO₂And reaction product is difficult to the problems such as separating and the process is caused to be difficult to sizable application.For first Alkane selective oxidation prepares methanol or formaldehyde, since the oxidation rate of target product methanol and formaldehyde is more faster than raw material methane, Cause the selectivity of reaction lower, does not have sizable application prospect substantially.

Guo Xiaoguang, packet letter and and its work being published on " Science " magazine in partner 2014 using new material very The drawback in the technical process such as methane oxidation coupling is avoided well.This new catalyst utilizes the " list of lattice confinement Iron " center " catalyst, due to the Fe active site not adjoined, methane can only adsorb dissociation above, with CH₃Free radical It is desorbed with H radical form, and CH₃Free radical it is subsequent enter gas phase, constituted via gas phase chain growth to be formed final product ethylene, The selectivity adduction of benzene and naphthalene, three is greater than 99%.

The catalyst test of laboratory scale generallys use quartz material reactor, this is because its inert nature, and easily In the processing of realization designated shape size, therefore it is widely used by laboratory scope.But its cost is higher, and mechanical strong Spend low, connection is difficult, can not push to industrialize.

The spies such as silicon carbide material has high temperature resistant, intensity is big, heating conduction is outstanding, corrosion-resistant, shock resistance, electric conductivity are good Property, therefore there is fabulous prospects for commercial application.

Summary of the invention

The present invention relates to a kind of silicon carbide reactor device and its application in the direct conversion process of methane anaerobic, the silicon carbide The material of reactor is metal-doped silicon carbide, and it is direct which realizes the methane anaerobic based on silicon carbide material reactor Conversion.The methane anaerobic conversion refers in free-dioxygen (O₂) or without elemental sulfur (S) or without oxysulfide (such as SO₂Deng) The mode for directly converting methane under the conditions of existing.

One aspect of the present invention provides a kind of preparation method of silicon carbide reactor device, the described method comprises the following steps:

Step 1 obtains to obtain mixture 1 using silicon carbide, metallic element, carbon source, silicon source, adhesive as raw material after mixing；

Through moulding, roasting, the silicon carbide reactor device is made in mixture 1 by step 2；

The metallic element be selected from lithium, sodium, potassium, magnesium, aluminium, calcium, strontium, barium, yttrium, lanthanum, titanium, zirconium, cerium, chromium, molybdenum, tungsten, rhenium, At least one of iron, cobalt, nickel, copper, zinc, germanium, indium, tin, lead, bismuth, preferably lithium, potassium, magnesium, aluminium, calcium, strontium, barium, titanium, cerium, manganese, cobalt, At least one of iron, nickel, zinc；

In raw material, the amount of silicon carbide is more than or equal to 50wt.%, is less than or equal to 99.9wt.%；Metallic element (conversion to gold Belong to simple substance) amount be more than or equal to 0.0001wt.%, be less than or equal to 10wt.%；The amount of carbon source (converting to carbon) is more than or equal to 0.0001wt.% is less than or equal to 30wt.%；The amount of silicon source (element silicon is arrived in conversion) is more than or equal to 0.0001wt.%, be less than etc. In 30wt.%；The silicon carbide is at least one of α-SiC, β-SiC powder；State existing for the metallic element is oxygen At least one of compound, carbide, nitride, silicide；The carbon source include graphite, carbon black, active carbon, in carbonitride It is at least one；The silicon source includes at least one of solid silicon source, liquid silicon source, metal silicide；The solid silicon source packet Include at least one of silica, silicon nitride, elemental silicon, metal silicide；The liquid silicon source is positive tetraethyl orthosilicate, silicon At least one of colloidal sol；The metal silicide include titanium silicide, zirconium silicide, tantalum silicide, tungsten silicide, palladium silicide, platinum silicide, At least one of cobalt silicide, molybdenum silicide, iron suicide, nickle silicide.

Wherein the effect of carbon source and silicon source is that silicon carbide is formed in situ after high-temperature roasting, is formed by high temperature direct in-situ Silicon carbide filling raw material silicon carbide gap, play the role of reduce porosity.

The silicon carbide reactor device moulding refers to for raw material being mixed and stirred for uniformly, carrying out extrusion by banded extruder Molding or design mold moldings formed therefrom, are then dried.The extruded moulding include screw rod extrusion and it is hydraulic squeeze Item is further to be uniformly mixed shaping raw material feeding banded extruder, is squeezed out material by the orifice plate spray head with certain diameter Afterwards, then it is cut into required length.Drying temperature is 10 degree~300 degree, and preferably 20~80 degree, humidity remains 0~40%, drying Time is 2 hours~10 days.

The silicon carbide powder partial size is 10nm~1mm as a preferred technical solution,；It is preferred that 50nm~500 μm, solid 10nm-200 μm of the partial size of silicon source；The liquid silicon source concentration 0.01~90%, concentration preferably 0.01~50%.

The heating rate of the roasting is 0.1~10 DEG C/min as a preferred technical solution, and treatment temperature is 1600 DEG C ~2200 DEG C, protective atmosphere is at least one of nitrogen, helium, argon gas, Krypton, xenon, air or oxygen, and pressure is 0.01bar~2bar, processing time are 24~240 hours；It also include a cooling process, cooling speed during the roasting Rate is 0.1~200 DEG C/min, and cooling atmosphere is at least one of inert gas, nitrogen, oxygen or air.

The roasting is carried out in high temperature furnace as a preferred technical solution, is also put in high temperature furnace in roasting process Enter accompaniment, the accompaniment is selected from least one of silicon, germanium, arsenic, tin, lead, aluminium, indium, sulphur, tellurium, bismuth.The work of accompaniment With being that vaporization at high temperature forms gas phase steam, it is further filled into the gap of silicon carbide skeleton reactor, reduces porosity.

It further include the process suppressed before roasting as a preferred technical solution, in the step 2, the pressure of compacting is 0.01~200MPa, preferably 10~180MPa, processing time are 10 minutes~2 days, preferably 2 hours~48 hours.Institute of the present invention State reactor compacting, refer to by the reactor after drying under the protection of mold, carry out HIGH PRESSURE TREATMENT make its entire body uniformly, Densification reaches good resistance to pressure and air-tightness.The preferred graphite material of the mold material, stainless steel material.

Further include as a preferred technical solution, auxiliary agent in the raw material of the step 1, the element of the auxiliary agent include phosphorus, At least one of boron, nitrogen, sulphur, silicon, germanium.The effect of auxiliary agent is by addition auxiliary agent to be combined with metallic atom, The charge for adjusting metallic atom, so that reactivity worth be adjusted.

Another aspect of the present invention also provides silicon carbide reactor device made from above-mentioned preparation method, and the material of the reactor is The silicon carbide of metallic element impurity；It is in terms of 100% by the final total weight of silicon carbide reactor device, the content of metallic element is big In being equal to 0.00001wt.%, it is less than or equal to 10wt.%；The content of auxiliary agent is 0~10wt%；The content of carbon source is 0.001wt%~40wt%；The content of silicon source is 0.001wt%~20wt%；The shape of the silicon carbide reactor device includes straight One of cast, U-tube, helix tube or two or more interconnections；The mouth-shaped of the silicon carbide reactor device includes Round, rectangular, triangle, ellipse are one or more kinds of to be used simultaneously；10 centimetres of the overall length of the silicon carbide reactor device~ 40 meters, internal diameter is 4~1000 millimeters, 2~50 millimeters of wall thickness.Preferably 10~200 millimeters of internal diameter, preferably 3~30 millimeters of wall thickness.Institute Stating metal lattice doping includes two processes of impurity and sintering, and the metallic element impurity refers to: by doping gold Belong to element to exchange with doped substrate element, other elements of doped metallic elements and doped substrate form (such as ionic bond) Or specified chemical key is not formed, it is restricted to doped metallic elements in the lattice of doped substrate, to generate specific catalysis Performance.

Further aspect of the present invention is to provide above-mentioned silicon carbide reactor device using methane as raw material direct catalytic reaction ethylene Application in technique.

The temperature of the catalysis reaction is 750~1300 DEG C as a preferred technical solution,；The raw material of the catalysis reaction Gas is methane or methane mixed gas；The methane mixed gas composition includes in addition to methane, further includes inert atmosphere gases Or one or both of non-inert atmosphere gas；The inert atmosphere gases be at least one of nitrogen, helium, argon gas, Volume content of the inert atmosphere gases in reactor feed gas is 0~95%；The non-inert atmosphere gas is carbon monoxide, hydrogen Gas, carbon dioxide, water, C_2-4Monohydric alcohol, C_2-4The mixture of one of alkane, alkene or two kinds or more；The non-inert gas The volume content of atmosphere gas and methane ratio is 0~10%；The volume content of methane is 1~100% in the unstrpped gas；It is described Be catalyzed reaction process propylene simultaneously, butylene, aromatic hydrocarbons and hydrogen, aromatic product include benzene, toluene, paraxylene, ortho-xylene, One of meta-xylene, ethylbenzene, naphthalene are a variety of.

The process of the catalysis reaction is that continuous flowing reaction pattern or period gas are cut as a preferred technical solution, Mold changing formula；Continuous flowing reaction pattern: catalytic reaction temperature is 750~1300 DEG C, preferably 900~1250 DEG C；Reaction pressure 0.1 ~1Mpa；The gas flow rate of reactor feed gas is 1.0~50L/min, preferably 4.0~20.0L/min；Period gas switches mould Formula: catalytic reaction temperature is 750~1300 DEG C, preferably 900~1250 DEG C；0.1~1Mpa of reaction pressure；The gas of reactor feed gas Body flow velocity is 1.0~50L/min, preferably 4.0~20.0L/min；Period switch mode be methane feed gas and inert purge gas, Regeneration gas carries out period switching, and regeneration gas includes 0.01%~99.99% H₂, 0.05%~50%O₂, 0.05%~50% CO, 0.05%~50%CO₂, 0.05%~50%H₂O, 0.05%~50%NH₃One of or two or more, regeneration gas Gas flow rate be 1.0~30L/min, preferably 2.0~10.0L/min, regenerate 0.1~1MPa of atmospheric pressure；Inert purge gas is protected One of helium, neon, argon, krypton, xenon, radon or two or more are protected, the mass space velocity of inert purge gas is 1.0~20L/min, excellent Select 4.0~15.0L/min.Switching time in period is methane (T1), inert purge gas (T2), regeneration gas (T3), wherein 0≤T1≤ 5000h,0≤T2≤240h,0≤T2≤240h。

Methane direct conversion studies have shown that should during activated centre be the activated centre Fe-2C-Si, be based on this, this hair Bright further research and development directly react metallic element with SiC material, so that activated centre is directly prepared, without anti- It answers and is formed in situ under atmosphere.

Type of the present invention and a kind of silicon carbide reactor device, the material of the reactor are the carbonization of metallic element impurity Silicon greatly reduces the radial temperature of reaction process using the good thermal conductivity and chemical reaction inert nature of the material Difference is based on the reactor direct synthesizing ethylene of catalytic methane under anaerobic, realizes to reduce the energy consumption of reaction process The nil product carbon and ethylene high selectivity of methane, the conversion ratio of methane are 10~70%；Ethylene selectivity is 40~75%； Propylene Selectivity is 5~15%；Arenes selectivity is 0~40%；Nil product carbon.

The process has redox and hydro-thermal under catalyst life long (>1000h), catalyst high temperature (<1700 DEG C) steady Qualitative good, methane conversion and ethylene selectivity height, nil product carbon, product are easily isolated, catalyst is without amplification, industrialization difficulty Small, the features such as process is reproducible, safe operation is reliable, has wide prospects for commercial application.

Detailed description of the invention

Fig. 1 is the preparation flow of silicon carbide reactor device of the present invention

Fig. 2 is reactor R2 inner wall proton fluorescence spectrum analysis made from embodiment 2

Fig. 3 is the chromatography FID figure of reactor R5 product analysis made from embodiment 5

Fig. 4 is the partial enlarged view of spectral line integral result lap (border circular areas) in Fig. 2

Fig. 5 is the chromatography TCD figure of reactor R5 product analysis made from embodiment 5

Fig. 3~5 are reaction result chromatography spectral line, wherein can analyze methane, ethylene, ethane, benzene, toluene, two on FID The reactants such as toluene, naphthalene and product；It can analyze the unstripped gas such as methane, hydrogen, nitrogen or product on TCD.

Specific embodiment

Embodiment below is only limitted to explain that the present invention, protection scope of the present invention should include in the whole of claim Hold, is not limited only to the present embodiment.

Embodiment 1

By 1kg SiC powder, 300g high purity graphite powder, 300g silicon powder, 20g ferric nitrate, 100mL epoxy resin, 100mL water into Row uniformly mixing, wherein SiC powder is α-SiC, and partial size is 100~400nm, 100 μm of silicon powder partial size, is sent into banded extruder and carries out extrusion Molding, molding reactor are straight pipe type, and 2 meters of length, outer diameter 35mm, internal diameter 25mm, 50 DEG C of Muffle furnaces are sent into after naturally dry 4 days Middle continuation drying dehumidification continues in N₂Protection under, handle 2 days in 2000 DEG C of high temperature furnaces, taken out after cooling, to reactor into The polishing of row surface fine, obtains reactor R1.

Embodiment 2

By 1kg SiC powder, 200g high purity graphite powder, 200g silicon powder, 20g iron chloride, 100mL epoxy resin, 100mL water into Row uniformly mixing, wherein SiC powder is α-SiC, and partial size is 300~1000nm, 100 μm of silicon powder partial size, is sent into banded extruder and is squeezed Item molding, molding reactor are straight pipe type, and 2 meters of length, outer diameter 15mm, internal diameter 5mm, 50 DEG C of Muffles are sent into after naturally dry 4 days Continue drying dehumidification in furnace, and then carry out compression process, pressing pressure 100Mpa, the pressing time is 30 minutes.Continue in N₂ Protection under, handle 3 days in 2000 DEG C of high temperature furnaces, taken out after cooling, to reactor carry out surface fine polishing, reacted Device R2.Fig. 2 is the proton fluorescence spectrogram of the reactor wall, and bright spot is Fe atom, shows that Fe distribution is very uniform.

Embodiment 3

By 1kg SiC powder, 100g carbon black powder, 100g silicon dioxide powder, 40g nickel chloride, 200mL epoxy resin, 200mL water It is uniformly mixed, wherein SiC powder is α-SiC, and partial size is 300~500 μm, 200 μm of silicon dioxide powder partial size, is sent into banded extruder Extruded moulding is carried out, molding reactor is straight pipe type, and 2 meters of length, outer diameter 25mm, internal diameter 15mm, naturally dry were sent into 50 after 4 days Continue drying dehumidification in DEG C Muffle furnace, continues in N₂Protection under, handle 4 days in 2000 DEG C of high temperature furnaces, taken out after cooling, it is right Reactor carries out surface fine polishing, obtains reactor R3.

Embodiment 4

By 1kg SiC powder, 50g high purity silicon nitride carbon dust, 100g silicon nitride, 100g cobalt chloride, 400mL epoxy resin, 200mL Water is uniformly mixed, and wherein SiC powder is α-SiC, and partial size is 100~200nm, is sent into banded extruder and is carried out extruded moulding, molding Reactor is straight pipe type, 2 meters of length, outer diameter 40mm, internal diameter 20mm, is sent into 250 DEG C of Muffle furnaces after naturally dry 4 days and continues to dry Dry dehumidifying, and then compression process, pressing pressure 180Mpa are carried out, the pressing time is 60 minutes.Continue in N₂Protection under, It handles 1 day in 1800 DEG C of high temperature furnaces, is taken out after cooling, surface fine polishing is carried out to reactor, obtains reactor R4.

Embodiment 5

By 1kg SiC powder, 100g activity powdered carbon, 400g silicon nitride powder, 200g silica powder, 200g zinc nitrate, 500mL ring Oxygen resin, 1000mL water are uniformly mixed, and wherein SiC powder is β-SiC, and partial size is 50~100nm, are sent into moulding machine and are cast Mold forming, molding reactor are U cast, and 2 meters of length, outer diameter 35mm, internal diameter 25mm, 150 DEG C of Muffles are sent into after naturally dry 4 days Continue drying dehumidification in furnace, continues in N₂Protection under, handle 2 days, taken out after cooling, to reactor in 1800 DEG C of high temperature furnaces Surface fine polishing is carried out, reactor R5 is obtained.

Embodiment 6

By 2kg SiC powder, 200g high purity graphite powder, 600g silicon powder, 100g iron suicide, 200mL epoxy resin, 1000mL water It is uniformly mixed, wherein SiC powder is β-SiC, and partial size is 500~900 μm, 300 μm of silicon powder partial size, is sent into moulding machine and is cast Mold forming, molding reactor are U cast, and 2 meters of length, outer diameter 15mm, internal diameter 5mm, 150 DEG C of Muffles are sent into after naturally dry 4 days Continue drying dehumidification in furnace, and then carry out compression process, pressing pressure 50Mpa, the pressing time is 60 minutes.Continue in N₂'s It under protection, handles 2 days in 2100 DEG C of high temperature furnaces, is taken out after cooling, surface fine polishing is carried out to reactor, obtains reactor R6。

Embodiment 7

By 2kg SiC powder, 100g high purity graphite powder, 50g silicon powder, 10g manganese nitrate, 100mL epoxy resin, 100mL water into Row uniformly mixing, wherein SiC powder is the 1:1 mixed powder of α-SiC and β-SiC, and partial size is 100~200nm, 100 μ of silicon powder partial size M, be sent into moulding machine carry out moldings formed therefrom, molding reactor be U cast, 2 meters of length, outer diameter 25mm, internal diameter 15mm, naturally dry It is sent into 50 DEG C of Muffle furnaces after 4 days and continues drying dehumidification, continued in N₂Protection under, handled 4 days in 2100 DEG C of high temperature furnaces, companion It is 100g silicon raw ore (purity > 90%) with object, is taken out after cooling, surface fine polishing is carried out to reactor, obtains reactor R7.

Embodiment 8

By 10kg SiC powder, 450g high purity graphite powder, 200g high purity silicon nitride carbon dust, 200g silicon powder, 120g nickle silicide, 200mL epoxy resin, 2000mL water are uniformly mixed, and wherein SiC powder is β-SiC, and partial size is 600~800nm, silicon powder partial size 150 μm, be sent into moulding machine carry out moldings formed therefrom, molding reactor be spiral cast, 2 meters of length, outer diameter 35mm, internal diameter 25mm, It is sent into 50 DEG C of Muffle furnaces after naturally dry 4 days and continues drying dehumidification, continued in N₂Protection under, in 1800 DEG C of high temperature furnaces Reason 2 days, accompaniment are the high-purity policrystalline silicon of 100g (purity > 95%), are taken out after cooling, carry out surface fine polishing to reactor, Obtain reactor R8.

Embodiment 9

1kg SiC powder, 300g high purity graphite powder, 300g silicon powder, 100mL epoxy resin, 100mL water are uniformly mixed It closes, wherein SiC powder is α-SiC, and partial size is 500~1000nm, it 100 μm of silicon powder partial size, is sent into moulding machine and carries out moldings formed therefrom, at Type reactor is spiral cast, and 2 meters of length, outer diameter 35mm, internal diameter 25mm, 50 DEG C of Muffle furnace relayings are sent into after naturally dry 4 days Continuous drying dehumidification, and then compression process, pressing pressure 200Mpa are carried out, the pressing time is 10 minutes.Continue in N₂Protection Under, it is handled 3 days in 1900 DEG C of high temperature furnaces, accompaniment is 100g high-purity silicon powder (purity > 95%), is taken out after cooling, to reaction Device carries out surface fine polishing, obtains reactor R9.

Embodiment 10

10kg SiC powder, 800g high purity graphite powder, 500g silicon powder, 100mL epoxy resin, 500mL water are uniformly mixed It closes, wherein SiC powder is α-SiC, and partial size is 300~400nm, it 100 μm of silicon powder partial size, is sent into moulding machine and carries out moldings formed therefrom, at Type reactor is spiral cast, and 2 meters of length, outer diameter 60mm, internal diameter 30mm, 50 DEG C of Muffle furnace relayings are sent into after naturally dry 4 days Continuous drying dehumidification, continues in N₂Protection under, handled 4 days in 2100 DEG C of high temperature furnaces, accompaniment be the high-purity silicon single crystal of 100g it is (pure Degree > 95%), it is taken out after cooling, surface fine polishing is carried out to reactor, obtains reactor R10.

Embodiment 11

By 1kg SiC powder, 300g high purity graphite powder, 300g silicon powder, 20g iron suicide, 100mL epoxy resin, 100mL water into Row uniformly mixing, wherein SiC powder is the 1:1 mixed powder of α-SiC and β-SiC, and partial size is 300~400nm, 100 μ of silicon powder partial size M, by mixture be sent into banded extruder carry out extruded moulding, molding reactor be straight pipe type, 2 meters of length, outer diameter 35mm, internal diameter 25mm is sent into 50 DEG C of Muffle furnaces after naturally dry 4 days and continues drying dehumidification, continues in N₂Protection under, in 2000 DEG C of high temperature It handles 2 days in furnace, is taken out after cooling, surface fine polishing is carried out to reactor, obtains reactor R11.

Embodiment 12

By 1kg SiC powder, 300g high purity graphite powder, the silica solution that 300g concentration is 50%, 20g ferric nitrate, 100mL epoxy Resin, 100mL water are uniformly mixed, and wherein SiC powder is the 10:1 mixed powder of α-SiC and β-SiC, partial size for 50~ 100nm, be sent into banded extruder carry out extruded moulding, molding reactor be straight pipe type, 2 meters of length, outer diameter 35mm, internal diameter 25mm, oneself It is sent into 50 DEG C of Muffle furnaces after so drying 4 days and continues drying dehumidification, continued in N₂Protection under, handled in 2000 DEG C of high temperature furnaces It 2 days, is taken out after cooling, surface fine polishing is carried out to reactor, obtains reactor R12.

Catalyst reaction evaluation

All reaction examples carry out in online micro-reaction device in situ, which is equipped with gas mass flow meter, gas (tail gas of reactor is directly connect with the proportional valve of chromatography, and it is real to carry out the period for body deoxidation dehydrating tube and online product analysis chromatography When sampling analysis).Reactor feed gas is by CH₄、N₂Gas composition, N are added with the second component₂As interior standard gas.Online product point Analysis is equipped with FID and TCD dual detector using Agilent 7890B gas-chromatography, and wherein fid detector is equipped with HP-1 capillary column Low-carbon alkene, low-carbon alkanes and aromatic hydrocarbons are analyzed；TCD detector is equipped with Hayesep D packed column to methane, hydrogen and interior Mark nitrogen is analyzed.Methane is calculated according to the Carbon balance of reaction front and back according to patent (CN1247103A, CN1532546A) Conversion ratio, carbonaceous products selectivity and carbon distribution.

The reactor R1-R12 prepared using embodiment 1~12, uses the air in 30ml/min Ar gas metathesis reactor After about 30 minutes, from room temperature with the heating rate temperature programming of 5 DEG C/min to following temperature and corresponding air speed, it is former to adjust reaction The air speed of gas is expected to following air speed, and methane conversion and each selectivity of product are as shown in the table.

1 reactor feed gas of table are as follows: 10vol.%N₂, 90vol.%CH₄

2 reactor feed gas of table are as follows: 10vol.%H₂, 10vol.%N₂, 80vol.%CH₄

Claims

1. a kind of preparation method of silicon carbide reactor device, which is characterized in that the described method comprises the following steps:

The silicon carbide reactor device is made by mixture 1 through moulding, roasting in step 2；

The metallic element be selected from lithium, sodium, potassium, magnesium, aluminium, calcium, strontium, barium, yttrium, lanthanum, titanium, zirconium, cerium, chromium, molybdenum, tungsten, rhenium, iron, cobalt, At least one of nickel, copper, zinc, germanium, indium, tin, lead, bismuth；

In raw material, the amount of silicon carbide is more than or equal to 50wt.%, is less than or equal to 99.9wt.%；The amount of metallic element is more than or equal to 0.0001wt.% is less than or equal to 10wt.%；The amount of carbon source is more than or equal to 0.0001wt.%, is less than or equal to 30wt.%；Silicon source Amount be more than or equal to 0.0001wt.%, be less than or equal to 30wt.%；

The silicon carbide is at least one of α-SiC, β-SiC powder；

State existing for the metallic element is at least one of oxide, carbide, nitride, silicide；

The carbon source includes at least one of graphite, carbon black, active carbon, carbonitride；

The silicon source includes at least one of solid silicon source, liquid silicon source, metal silicide；The solid silicon source includes dioxy At least one of SiClx, silicon nitride, elemental silicon, metal silicide；The liquid silicon source be positive tetraethyl orthosilicate, in silica solution At least one；The metal silicide includes titanium silicide, zirconium silicide, tantalum silicide, tungsten silicide, palladium silicide, platinum silicide, silication At least one of cobalt, molybdenum silicide, iron suicide, nickle silicide.

2. preparation method according to claim 1, which is characterized in that the silicon carbide powder partial size is 10nm~1mm；Gu 10nm-200 μm of the partial size of body silicon source；The liquid silicon source concentration 0.01~90%.

3. preparation method according to claim 1, which is characterized in that the heating rate of the roasting be 0.1~10 DEG C/ Min, treatment temperature are 1600 DEG C~2200 DEG C, and protective atmosphere is nitrogen, in helium, argon gas, Krypton, xenon, air or oxygen At least one, pressure are 0.01bar~2bar, and the processing time is 24~240 hours；

It also include a cooling process during the roasting, rate of temperature fall is 0.1~200 DEG C/min, and cooling atmosphere is lazy At least one of property gas, nitrogen, oxygen or air.

4. preparation method according to claim 1, which is characterized in that the roasting is carried out in high temperature furnace, is roasted Accompaniment is also put into journey in high temperature furnace, the accompaniment is in silicon, germanium, arsenic, tin, lead, aluminium, indium, sulphur, tellurium, bismuth It is at least one.

5. preparation method according to claim 1, which is characterized in that further include compacting before roasting in the step 2 Process, the pressure of compacting is 0.01~200MPa, and the processing time is 10 minutes~2 days.

6. preparation method according to claim 1, which is characterized in that it further include auxiliary agent in the raw material of the step 1, institute The element for stating auxiliary agent includes at least one of phosphorus, boron, nitrogen, sulphur, silicon, germanium.

7. silicon carbide reactor device made from preparation method described in claim 1-6 any one, which is characterized in that the reactor Material be metallic element impurity silicon carbide；It is metallic element in terms of 100% by the final total weight of silicon carbide reactor device Content be more than or equal to 0.00001wt.%, be less than or equal to 10wt.%；The content of auxiliary agent is 0~10wt%；The content of carbon source is 0.001wt%~40wt%；The content of silicon source is 0.001wt%~20wt%；

The shape of the silicon carbide reactor device includes one of straight pipe type, U-tube, helix tube or two or more mutually interconnection It connects；The mouth-shaped of the silicon carbide reactor device uses simultaneously including round, rectangular, triangle, ellipse one or more；

10 centimetres~40 meters of the overall length of the silicon carbide reactor device, internal diameter are 4~1000 millimeters, 2~50 millimeters of wall thickness.

8. silicon carbide reactor device described in claim 7 is using methane as the application in raw material direct catalytic reaction ethylene process.

9. application according to claim 8, which is characterized in that the temperature of the catalysis reaction is 750~1300 DEG C；

The unstrpped gas of the catalysis reaction is methane or methane mixed gas；

Methane mixed gas composition includes in addition to methane, further includes one in inert atmosphere gases or non-inert atmosphere gas Kind or two kinds；

The inert atmosphere gases are at least one of nitrogen, helium, argon gas, and inert atmosphere gases are in reactor feed gas Volume content is 0~95%；

The non-inert atmosphere gas is carbon monoxide, hydrogen, carbon dioxide, water, C_2-4Monohydric alcohol, C_2-4In alkane, alkene One or two or more kinds of mixtures；

The volume content ratio of the non-inert atmosphere gas and methane is 0~10%；

The volume content of methane is 1~100% in the unstrpped gas；

It is described catalysis reaction process propylene simultaneously, butylene, aromatic hydrocarbons and hydrogen, aromatic product include benzene, toluene, paraxylene, One of ortho-xylene, meta-xylene, ethylbenzene, naphthalene are a variety of.

10. application according to claim 9, which is characterized in that the process of the catalysis reaction is continuous flowing reactive mould Formula or period gas switch mode；

Continuous flowing reaction pattern: catalytic reaction temperature is 750~1300 DEG C；0.1~1Mpa of reaction pressure；Reactor feed gas Gas flow rate is 1.0~50L/min；

Period gas switch mode: catalytic reaction temperature is 750~1300 DEG C；0.1~1Mpa of reaction pressure；Reactor feed gas Gas flow rate is 1.0~50L/min；

Period switch mode is methane feed gas and inert purge gas, regeneration gas carry out period switching, and regeneration gas includes 0.01% ~99.99% H₂, 0.05%~50%O₂, 0.05%~50%CO, 0.05%~50%CO₂, 0.05%~50%H₂O, 0.05%~50%NH₃One of or it is two or more, the gas flow rate of regeneration gas is 1.0~30L/min, regenerates atmospheric pressure 0.1~1MPa；One of inert purge gas shielded helium, neon, argon, krypton, xenon, radon are two or more, the matter of inert purge gas Amount air speed is 1.0~20L/min.Switching time in period is methane (T1), inert purge gas (T2), regeneration gas (T3), wherein 0≤ T1≤5000h,0≤T2≤240h,0≤T2≤240h。