CN108452822A - It is a kind of to prepare higher olefins catalyst and Catalytic processes by the microwave radiation technology of carrier of MCM-41 - Google Patents
It is a kind of to prepare higher olefins catalyst and Catalytic processes by the microwave radiation technology of carrier of MCM-41 Download PDFInfo
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- CN108452822A CN108452822A CN201810243747.8A CN201810243747A CN108452822A CN 108452822 A CN108452822 A CN 108452822A CN 201810243747 A CN201810243747 A CN 201810243747A CN 108452822 A CN108452822 A CN 108452822A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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- C07C2/24—Catalytic processes with metals
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- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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Abstract
The microwave radiation technology that the invention discloses a kind of with MCM 41 for carrier prepares higher olefins catalyst and Catalytic processes, and it is nickel molybdenum composite catalyst with MCM 41 for carrier that wherein microwave radiation technology methane, which directly prepares higher olefins with catalyst,；Under the conditions of Microwave-assisted firing and induction, hydrogen are excessive, methane is first through nickel powder catalytic dehydrogenation coupling and then through nickel molybdenum composite catalyst catalytic oligomerization, oligomerization product polycondensation under the action of heating and nickel molybdenum composite catalyst after rectification and purification, high selectivity higher olefins liquid fuels.The method of the present invention is using natural gas or biological methane as starting material, have the characteristics that higher olefins high selectivity, environmental-friendly, energy saving, of low cost, catalyst is nontoxic, free of contamination, is the most promising process route for preparing high-knock rating gasoline liquid fuel.
Description
Technical field
Higher olefins catalyst and Catalytic processes being prepared by the microwave radiation technology of carrier of MCM-41 the present invention relates to a kind of,
Belong to catalytic synthetic techniques field.
Background technology
Higher olefins such as C8 and C12 alkene is fine chemistry industry important intermediate, and wherein C8 alkene such as isooctene is by adding hydrogen
After can obtain isooctane, and the by-product that isooctane usually produces ethylene from petroleum cracking is obtained by chemical process derivative, with
The continuous reduction and exhaustion of petroleum reserves, the methane dehydrogenation that potential substitute will come from natural gas or biogas are coupled.Due to
The main component of natural gas is methane, and methane is highly stable, generates ethylene, acetylene, aromatic hydrocarbons and high-carbon hydrocarbon need 1273K or more
High reaction temperature.Although high reaction temperature is conducive to high conversion, such as methane conversion is up to 50%, temperature height, meeting
Cause product to decompose carbon distribution, there is high energy consumption and the undesirable result of environment.In in the past few decades, environmental-friendly methane is de-
Hydrogen oligomerization process causes extensive concern, such as prepares acetylene and ethylene, Qian Zhewei using microwave and plasma discharging teclmiques
Wave is gradually popularized in industry heating, plays efficient, accurate heating, energy saving and environmental-friendly effect.
Methane dehydrogenation produces higher olefins compound, although many reports in document are directed to use microwave or plasma
Body discharge technology, but use the MCM-41 being efficiently easy to get as carrier, under the action of microwave energy, using methane as starting
Raw material, by catalytic dehydrogenation coupling, catalytic oligomerization, separating-purifying, catalyzed polycondensation synthesize higher olefins, such as synthesize C8 isooctenes and
The catalyst of C12 olefin liquid products and technique are from having no document and patent report.
Higher olefins isooctene hydrogenation products isooctane is high-octane gasoline reconciliation raw material, and octane number is gasoline weight
The quality index wanted, addition anti-knock agent is the main method for improving octane number, and octane number is higher, and anti-knock is stronger.Vapour
Oily anti-knock agent is mainly used for reducing gasoline knocking, and the high gasoline of knock tendency can cause engine damage, deterioration of emission etc., because
This gasoline anti-knock agent is indispensable additive in gasoline.The isooctane obtained is converted from natural gas, octane number is higher, contains
Sulfur content is low, not oxygen-containing, and vapour pressure is also very low, meets state four, five standard of state, is examined from many-sided synthesis such as performance, environmental protection, price
Consider, the comprehensive performance of isooctane is widely used far better than other gasoline additives in America and Europe, but domestic use is not yet
It is universal, it is in the starting stage, future development has a high potential.
Invention content
The present invention is intended to provide a kind of preparing higher olefins catalyst and catalysis by the microwave radiation technology of carrier of MCM-41
Technique.Catalyst of the present invention is the nickel molybdenum composite catalyst using MCM-41 as carrier, using methane as starting material, by dehydrogenation idol
Higher olefins are made in conjunction, oligomerisation, catalyzed polycondensation three-step reaction.The method of the present invention has isooctene high selectivity, environmental-friendly, section
Energy, feature of low cost, isooctene hydrogenation products isooctane, the natural gas or biological methane are starting material, synthetic gasoline
The route of additive liquid fuel is most promising process route.
The present invention prepares higher olefins catalyst by the microwave radiation technology of carrier of MCM-41, is using MCM-41 as carrier
Nickel molybdenum composite catalyst, preparation method include the following steps：
Nickelous nitrate hexahydrate, ammonium heptamolybdate tetrahydrate and gas generation agent are dissolved in the deionized water of 5~10 times of quality respectively
In, it is dispersed with stirring uniformly, mixing obtains the aqueous metal salt containing gas generation agent；MCM-41 carriers are immersed into gained metal brine
Impregnate 16 in solution, at 80~90 DEG C~for 24 hours, 8~10h then are dehydrated in 90 DEG C, dry 8~16h at 110~120 DEG C,
Then 4~8h is calcined in 500~550 DEG C in air atmosphere to obtain to remove water, oxygen, nitrogen dioxide and carbon dioxide
NiO-MoO3/ MCM-41 composite catalysts；By gained NiO-MoO3/ MCM-41 composite catalysts are placed in hydrogen atmosphere, in 600
1~2h of hydrogenating reduction, obtains NiO at~700 DEG Cx-MoOy/ MCM-41 composite catalysts, wherein x=0~1, y=0~3.
The aperture 3.5nm of the MCM-41 carriers, specific surface 900m2/ g, total silicon, hole hold 0.80cm3/ g, relative crystallinity
90%, sodium content 0.1%, 3 μm, bulk density 1000g/ml of granularity, active principle content 99.99%, moisture content 0.1%, burn
Subtract 5%.
The gas generation agent is citric acid, oxalic acid or tartaric acid.
When hydrogenating reduction, hydrogen gas rate is 6~120mL/min.
The adding proportion of Nickelous nitrate hexahydrate, ammonium heptamolybdate tetrahydrate and gas generation agent is with the molar ratio of Ni, Mo, gas generation agent
It is calculated as 1:0.1~1.0:1.0~2.0.
NiOx-MoOyIn/MCM-41 composite catalysts, Ni metallic atom mass contents be 0~15%, preferably 6~
15%；Mo metallic atom mass contents are 0~15%, preferably 6~15%.
Higher olefins are directly prepared using catalyst microwave radiation technology methane of the present invention, are included the following steps：
Under the conditions of Microwave-assisted firing and induction, hydrogen are excessive, methane first through nickel powder catalytic dehydrogenation coupling, pass through again
Nickel molybdenum composite catalyst catalytic oligomerization, oligomerization product butylene contract after rectification and purification under the catalysis of nickel molybdenum composite catalyst
Poly- reaction, high selectivity higher olefins dimer C8 and tripolymer C12 liquid fuels.
The Microwave-assisted firing and induction are carried out in microwave reactor, and wavelength is 0.1~100cm, and frequency is
300GHz~300MHz, power are 300~3000W.
The volume ratio of hydrogen and methane is 3~10：1, preferably 3-5:1；The gas stagnation pressure of hydrogen and methane be 0.1~
1.0MPa。
Nickel powder purity is 99.0~99.999%.
Polycondensation reaction 0.3~2.0MPa of pressure, 80~280 DEG C of temperature.
Dehydrogenation coupling of the present invention and oligomerization catalysis reaction carry out in microwave reactor, and one section is used in microwave reactor
Interior filling nickel powder catalyst is managed, is also in two sections of fixed beds wherein being quartz glass tube in one section of fixed bed with two sections of fixed beds
Quartz glass tube manages interior filling NiOx-MoOy/ MCM-41 composite catalysts, product gained butylene after separating-purifying, enter
Third section stainless steel tubular reactor polycondensation, stainless steel tube is interior to fill NiOx-MoOy/ MCM-41 composite catalysts, polycondensation reaction pressure
0.3~2.0MPa of power, 80~280 DEG C of temperature.
MCM-41 be a kind of novel nano structural material, duct can be in six side's ordered arrangements, uniform in size, aperture
It is continuously adjusted within the scope of 2-10nm, one-dimensional channels architecture, is the long-range order mesoporous material with uniform aperture, there is pole
High BET specific surface area~1000m2The characteristics of/g and big adsorption capacity~0.7ml/g, big adsorption capacity, uniform mesoporous knot
The features such as structure, than the quick diffusion that the poromerics such as zeolite and aluminophosphates are more advantageous to organic molecule, this enables it to be big
Heavy oil organic molecule select type reaction and provides unrivaled advantageous space and effectively in molecule especially petrochemical process
Acid activated centre, can adjustment aperture and acid concentration and intensity as needed, this molecular sieve analog can be used for Residue Catalytic Cracking,
Heavy-oil hydrogenation, lube oil hydrogenation, alkylation, olefinic polymerization, CO2With CH4The acid catalysis field and petrochemical industry such as separation separation
Process also has higher answer in fields such as heterogeneous catalysis, ion exchange, sensing technology, adsorbing separation and Advanced Inorganic materials
With value.
The present invention with cheap methane (coming from natural gas and biological methane) for raw material, methane in microwave heating and
Nickel powder dehydrogenation coupling, nickel molybdenum composite catalyst catalytic oligomerization are first passed through under induction, products therefrom butylene is compound in nickel molybdenum after purification
Polycondensation reaction is carried out under catalyst action, crude product of the reaction product liquid phase part containing isooctene passes through rectifying, obtains purity>98%
Isooctene liquid fuel.The method of the present invention has process route short, and environmental-friendly, with good investment, energy-saving, catalyst is without corruption
Erosion, free of contamination feature.
The present invention uses methane/hydrogen gas mixture, in nickel powder and NiOx-MoOyThe presence of/MCM-41 composite catalysts
Under, methane through microwave-excitation nickel catalytic dehydrogenation coupling, nickel molybdenum catalytic oligomerization, isolate and purify after, nickel molybdenum catalyst effect under two
Aggregate into higher olefins liquid fuel.The conversion ratio of the method for the present invention methane is 80%, and the selectivity for intermediate butylene is
99%.By gas-chromatography/electron impact ionization/mass spectrum (GC/EI/MS), analysis shows, butylene polycondensation conversion ratio is 85.3%,
Dimer C8 isooctene contents are 81.4 (weight) %, remaining liquid component is that tripolymer C12 olefin(e) centents are 18.6 (weights
Amount) %.The present invention is using methane as starting material, by dehydrogenation coupling, oligomerisation and polycondensation, the method for high selectivity isooctene
With significant novelty, has potential prospects for commercial application.
Specific implementation mode
The microwave reactor used in the embodiment of the present invention by two segment length is 200 millimeters, internal diameter is 10 millimeters, wall thickness
The cylindrical quartz glass pipe of 1.5mm forms, and microwave reactor power is 700w, microwave frequency 2.45GHz.Third section is fixed
Bed reactor, is made of the cylindrical stainless steel tube that length is 200 millimeters, internal diameter is 10 millimeters, using heat supply outside pipe.
Embodiment 1：The preparation of nickel-molybdenum/MCM-41 composite catalysts
By 0.0153mol Nickelous nitrate hexahydrates (purity 99.0%), 0.0094mol ammonium heptamolybdate tetrahydrate (purity
99.98%) it is dissolved in 30ml deionized waters, is stirred at room temperature 30 minutes respectively with 0.0306mol citric acids, obtain metal salt
Aqueous solution；By 8.212g MCM-41 (purity 99.0%) immerse gained aqueous metal salt in, 16h is impregnated at 80 DEG C, then in
90 DEG C of dehydration 8h, dry 8h, then calcines 8h, to remove water, oxygen and two in air atmosphere in 500 DEG C at 120 DEG C
Nitrogen oxide obtains NiO-NiMoO4(0.6277:1.0mol)/MCM-41 composite catalysts；By gained NiO-NiMoO4/MCM-41
Composite catalyst is placed in hydrogen atmosphere, and hydrogen feed flow rate is 60mL/min, and hydrogenating reduction 1h, obtains Ni- at 700 DEG C
Mo/MCM-41 composite catalysts.Nickel and molybdenum content are respectively 9 (weight) % in gained composite catalyst.
Embodiment 2：The methyl hydride catalyzed synthesis higher olefins of microwave radiation technology
Two sections of catalysis reactions of the present invention carry out in microwave reactor, and microwave reactor uses two sections of fixed beds, wherein
Be quartz glass tube in one section of fixed bed, manage in fill nickel powder catalyst, be also quartz glass tube in two sections of fixed beds, specification with
One section identical, manages interior filling Ni-Mo/MCM-41 composite catalysts, after rectifying detaches, gained butylene enters second-stage reaction product
Three-section fixed-bed stainless steel tubular reactor, reactor is interior to fill Ni-Mo/MCM-41 composite catalysts.
In microwave reactor, make methane (content 99.9%)-hydrogen (content 99.999%) mixed gas (CH4:H2=1：
5v/v) pass through teflon pipe.Methane-hydrogen gas mixture inlet pressure is 0.1~0.3MPa, and the inlet flow rate of methane is
The inlet flow rate of 10ml/min, hydrogen are 50ml/min.Microwave reactor is set as microwave heating 30 minutes under 700W, rear to continue
Extend 30 minutes.Mixed gas first flows through one filled with Ni powder (grey irregular powder, purity 99.999%) catalyst
Section fixed bed；Intermediate gas (ethylene) continues to flow through two sections of fixed beds (Ni-Mo/MCM-41 prepared filled with embodiment 1
Composite catalyst), product gas is passed through in the cold-trap (~30 DEG C) of the solution containing frozen ethanol, and butylene liquid is collected after condensation is cooling
Body, after rectification and purification, gained butylene is pumped into polycondensation in third section stainless steel tubular reactor, is filled in stainless steel tube real
The Ni-Mo/MCM-41 composite catalysts of the preparation of example 1, polycondensation reaction 0.3~2.0MPa of pressure are applied, temperature is 80~280 DEG C, instead
After answering, after gas-liquid separation, top unreacting material gas butylene returns to feed inlet cycle, switches by six-way valve,
It is analyzed into thermal conductivity detector (TCD)；Bottom liquid product is analyzed by hydrogen flame detector, using 2060 type gas chromatograph GC-
TCD-FID on-line checkings, methane conversion 80%, the selectivity for intermediate butylene is 99%, after condensation is cooling, collection liquid
Body product, is analyzed using GC/EI/MS, and the conversion ratio of butene dimerization is 85.3%, and dimer C8 isooctene contents are 81.4 (weights
Amount) %, remaining liquid component is that tripolymer C12 olefin(e) centents are 18.6 (weight) %.
Embodiment 3：The preparation of nickel-molybdenum/MCM-41 composite catalysts
By 0.0102mol Nickelous nitrate hexahydrates (purity 99.0%), 0.0063mol (Mo)) ammonium heptamolybdate tetrahydrate is (pure
99.98%) degree is dissolved in 0.0204mol oxalic acid in 16ml deionized waters respectively, be stirred at room temperature 60 minutes, obtains metal salt
Aqueous solution；By 8.800g MCM-41 (purity 99.0%) immerse gained aqueous metal salt in, impregnated at 80 DEG C for 24 hours, then in
90 DEG C of dehydration 16h, the dry 16h at 120 DEG C then calcine 6h in air atmosphere in 550 DEG C, with remove water, oxygen and
Nitrogen dioxide obtains NiO-NiMoO4(0.6277:1.0mol)/MCM-41 composite catalysts；Gained nickel-molybdenum/MCM-41 is multiple
It closes catalyst to be placed in hydrogen atmosphere, hydrogen feed flow rate is 60mL/min, and hydrogenating reduction 2h, obtains Ni-Mo/ at 700 DEG C
MCM-41 composite catalysts.The diameter of gained composite catalyst particle is about 200nm, and nickel and molybdenum content are respectively in composite catalyst
6 (weight) %.
Embodiment 4：Microwave radiation technology methane is for higher olefins
Two sections of catalysis reactions of the present invention carry out in microwave reactor, and microwave reactor uses two sections of fixed beds, wherein
Interior one section of fixed bed is quartz glass tube, manages interior filling pure nickel powder catalyst, is also quartz glass tube in two sections of fixed beds, in pipe
Ni-Mo/MCM-41 composite catalysts are filled, for two sections of products after rectifying detaches, gained butylene enters three-section fixed-bed stainless steel
Polycondensation in reaction tube, stainless steel tube is interior to fill Ni-Mo/MCM-41 composite catalysts.
In microwave reactor, make methane (content 99.9%)-hydrogen (content 99.999%) mixed gas (CH4:H2=1：
5v/v) pass through teflon pipe.Methane-hydrogen gas mixture inlet pressure is 0.1~0.3MPa, and the inlet flow rate of methane is
The inlet flow rate of 20ml/min, hydrogen are 100ml/min.Microwave reactor is set as microwave heating 60 minutes under 700W.Mixing
Gas first flows through one section of fixed bed filled with Ni powder (grey irregular powder, purity 99.999%) catalyst；Centre production
Object gas (ethylene) continue to flow through two sections of fixed beds (filled with embodiment 3 prepare Ni-Mo/MCM-41 composite catalysts), two
Product mixtures are then passed through in the cold-trap (~30 DEG C) of the solution containing frozen ethanol by section product, after condensation is cooling, collect butylene
Product liquid.
Gained butylene is pumped into three-section fixed-bed stainless steel reaction pipe after rectifying detaches, and manages interior filling embodiment 3 and prepares
Ni-Mo/MCM-41 composite catalysts, 0.3~2.0Mpa of reaction pressure, temperature be 80~280 DEG C, after reaction, do not turn
The product gas of change recycles, and is analyzed using thermal conductivity detector (TCD) after six-way valve switches, and the product liquid of collection is mainly two
Aggressiveness and tripolymer.It is detected by hydrogen flame, using 2060 type gas chromatograph on-line analyses, methane conversion 60%, for
The selectivity of butylene is 99%.It is analyzed using GC/EI/MS, butylene polycondensation conversion ratio is 77.1%, dimer C8 isooctene contents
For 78.5 (weight) %, remaining liquid component is that tripolymer C12 olefin(e) centents are 21.5 (weight) %.
Claims (10)
1. a kind of preparing higher olefins catalyst by the microwave radiation technology of carrier of MCM-41, it is characterised in that：It is with MCM-41
For the nickel molybdenum composite catalyst of carrier, it is abbreviated as NiOx-MoOy/ MCM-41 composite catalysts, wherein x=0~1, y=0~3；
NiOx-MoOyIn/MCM-41 composite catalysts, Ni metallic atom mass contents are that 0~15%, Mo metallic atom mass contents are 0
~15%.
2. a kind of preparation side described in claim 1 preparing higher olefins catalyst using MCM-41 as the microwave radiation technology of carrier
Method, it is characterised in that include the following steps：
Nickelous nitrate hexahydrate, ammonium heptamolybdate tetrahydrate and gas generation agent are dissolved in respectively in the deionized water of 5~10 times of quality, stirred
It mixes and is uniformly dispersed, mix, obtain the aqueous metal salt containing gas generation agent；MCM-41 carriers are immersed into gained aqueous metal salt
In, impregnate 16 at 80~90 DEG C~for 24 hours, 8~10h then are dehydrated in 90 DEG C, dry 8~16h at 110~120 DEG C, then
4~8h is calcined in 500~550 DEG C obtain NiO- to remove water, oxygen, nitrogen dioxide and carbon dioxide in air atmosphere
MoO3/ MCM-41 composite catalysts；By gained NiO-MoO3/ MCM-41 composite catalysts are placed in hydrogen atmosphere, in 600~700
1~2h of hydrogenating reduction at DEG C, obtains NiOx-MoOy/ MCM-41 composite catalysts.
3. preparation method according to claim 2, it is characterised in that：
The aperture 3.5nm of the MCM-41 carriers, specific surface 900m2/ g, total silicon, hole hold 0.80cm3/ g, relative crystallinity 90%,
Sodium content 0.1%, 3 μm, bulk density 1000g/ml of granularity, active principle content 99.99%, moisture content<0.1%, igloss<
5%.
4. preparation method according to claim 2, it is characterised in that：
The gas generation agent is citric acid, oxalic acid or tartaric acid.
5. preparation method according to claim 2, it is characterised in that：
When hydrogenating reduction, hydrogen gas rate is 6~120mL/min.
6. preparation method according to claim 2, it is characterised in that：
The adding proportion of Nickelous nitrate hexahydrate, ammonium heptamolybdate tetrahydrate and gas generation agent is with the molar ratio computing of Ni, Mo, gas generation agent
1:0.1~1.0:1.0~2.0.
7. using catalyst microwave radiation technology methane described in claim 1 for the Catalytic processes of higher olefins, it is characterised in that
Include the following steps：
Under the conditions of Microwave-assisted firing and induction, hydrogen are excessive, methane is first through nickel powder catalytic dehydrogenation coupling, again through nickel molybdenum
Composite catalyst catalytic oligomerization, progress polycondensation is anti-under the catalysis of nickel molybdenum composite catalyst after rectification and purification for oligomerization product butylene
It answers, high selectivity higher olefins dimer C8 and tripolymer C12 liquid fuels.
8. Catalytic processes according to claim 7, it is characterised in that：
The Microwave-assisted firing and induction are carried out in microwave reactor, and wavelength is 0.1~100cm, frequency 300GHz
~300MHz, power are 300~3000W.
9. Catalytic processes according to claim 7, it is characterised in that：
The volume ratio of hydrogen and methane is 3~10：1；The gas stagnation pressure of hydrogen and methane is 0.1~1.0MPa.
10. Catalytic processes according to claim 7, it is characterised in that：
Polycondensation reaction 0.3~2.0MPa of pressure, 80~280 DEG C of temperature.
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| CN114534770A (en) * | 2022-01-06 | 2022-05-27 | 深圳大学 | Preparation of catalyst with wave-absorbing-catalyzing function and application of microwave pyrolysis of sludge |
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| CN114534770A (en) * | 2022-01-06 | 2022-05-27 | 深圳大学 | Preparation of catalyst with wave-absorbing-catalyzing function and application of microwave pyrolysis of sludge |
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