CN110090532A - A kind of near-zero release carbon material preparation process of UF membrane coupling lighter hydrocarbons thermal decomposition - Google Patents
A kind of near-zero release carbon material preparation process of UF membrane coupling lighter hydrocarbons thermal decomposition Download PDFInfo
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- CN110090532A CN110090532A CN201910284246.9A CN201910284246A CN110090532A CN 110090532 A CN110090532 A CN 110090532A CN 201910284246 A CN201910284246 A CN 201910284246A CN 110090532 A CN110090532 A CN 110090532A
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- thermal decomposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- C—CHEMISTRY; METALLURGY
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
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Abstract
The present invention provides a kind of near-zero release carbon material preparation processes of UF membrane coupling lighter hydrocarbons thermal decomposition, belong to technical field of new material preparation.The technique is from the most worthy downstream whereabouts of the component characteristic of lighter hydrocarbons Catalytic Thermal Decomposition tail gas, each component, hydrogen membrane separation technique is coupled with lighter hydrocarbons Catalytic Thermal Decomposition device, tail gas is thermally decomposed using membrane separation, it seeps residual air and returns to preheating furnace and pyrolysis pipe, reduce the dosage of carbon source and nitrogen, fuel of the infiltration gas as preheating furnace rich in hydrogen, reduces the dosage of fuel gas.Due to fully and rationally using for thermal decomposition tail gas each component, using the carbon material preparation process of lighter hydrocarbons Catalytic Thermal Decomposition route, near-zero release not only may be implemented, but also cost can be significantly reduced.By taking propylene Catalytic Thermal Decomposition process as an example, the gaseous carbon source dosage of UF membrane coupling technique can reduce 21.6%, and nitrogen use level can reduce 92.0%, and fuel gas dosage can save 80% or more.
Description
Technical field
The present invention relates to a kind of near-zero release carbon material preparation processes of UF membrane coupling lighter hydrocarbons thermal decomposition, belong to new material
Preparation technical field.The technique handles mixed gas hydrogen/lighter hydrocarbons/nitrogen of thermal decomposition process by-product using hydrogen membrane separation technique
Gas, the infiltration residual air lighter hydrocarbons and nitrogen of acquisition return to preheating furnace and pyrolysis pipe, reduce carbon source and protect the dosage of nitrogen, obtain
The infiltration gas obtained is rich in fuel of the hydrogen as preheating furnace, reduces the dosage of fuel gas.It is light by membrane separation technique comprehensive utilization
Hydrocarbon thermally decomposes the tail gas of by-product, and the near-zero release of lighter hydrocarbons thermal decomposition process may be implemented.
Background technique
With the invention of numerous super carbon materials such as fullerene, carbon fiber, carbon nanotube, graphene and graphite alkene, 20
Century is considered as the The Carbon Age carbon epoch.By taking carbon nanotube as an example, radial dimension is nanoscale, and axial dimension is
Micron order has excellent mechanics, electricity and chemical property, can be used for manufacturing high-strength material, low electrical resistant material etc..With stone
For black alkene, the computer speed of service limit of silicon device is the Gigahertz order of magnitude, and the computer of graphene device is reachable
To 1000 times of this speed.
The preparation method of super carbon material mainly has arc discharge method, laser evaporization method and catalytic decomposition method.Wherein,
Catalytic decomposition method is that gaseous carbon source by the immobilized template for having catalyst and decomposes generation carbon materials under the conditions of 800~1200 DEG C
Material.Common gaseous carbon source includes methane, ethylene, propylene and benzene etc..In order to control the morphology and size of carbon material, gaseous carbon source
In need to be added appropriate inert nitrogen gas come regulate and control reaction.It is compared with other methods, catalytic decomposition method operation temperature is lower,
Succinct easily-controllable, strong applicability is easy amplification, is the prevailing technology technology of super carbon material large-scale production.
The hydrogen containing tail gas of 1 Catalytic Thermal Decomposition different carbon source by-product of table
For using lighter hydrocarbons as the Catalytic Thermal Decomposition technique of carbon source, a large amount of hydrogen of by-product while forming super carbon material.
When using methane as carbon source, the hydrogen of every kilogram of carbon material by-product is about 3.74 mark sides；When using alkene as carbon source, every kilogram of carbon material
The hydrogen of by-product is about 1.86 mark sides；When using benzene as carbon source, the hydrogen of every kilogram of carbon material by-product is about 0.94 mark side.In order to protect
The material balance in reaction tube is held, Catalytic Thermal Decomposition process need to discharge a large amount of hydrogen containing tail gas.Catalytic Thermal Decomposition different carbon source by-product
Hydrogen containing tail gas composition and yield be shown in Table 1.For producing the typical catalyst thermal decomposer of 1000 tons of super carbon materials, tail gas per year
Yield will be up to 2.0~7.1 million mark sides/year.Due to containing a large amount of hydro carbons in Catalytic Thermal Decomposition tail gas, direct emission will be caused
Serious atmosphere pollution, it is therefore necessary to which harmless treatment is carried out to it.A kind of feasible detoxification method is will to thermally decompose tail gas
Directly as the fuel of preheating furnace, but due to nitrogen content height, the flame temperature in preheating furnace is significantly reduced, efficiency of combustion is low.
In conclusion preparing the production technology of carbon material as gaseous carbon source, by Catalytic Thermal Decomposition using lighter hydrocarbons, a kind of efficient heat is needed
Decomposed tail gas processing technique fully and rationally uses hydrogen, the lighter hydrocarbons in tail gas while reducing discharge, reducing environmental pollution
And nitrogen, reduce the cost that Catalytic Thermal Decomposition prepares super carbon material.
Summary of the invention
The purpose of the present invention is to provide a kind of near-zero release carbon material preparations of UF membrane coupling lighter hydrocarbons Catalytic Thermal Decomposition
Technique.The technique is led to from the most worthy downstream whereabouts of the component characteristic of lighter hydrocarbons Catalytic Thermal Decomposition tail gas and each component
It crosses hydrogen film separation unit to couple with lighter hydrocarbons Catalytic Thermal Decomposition unit, tail gas is thermally decomposed using membrane separation, more than the infiltration of acquisition
Gas lighter hydrocarbons and nitrogen return to preheating furnace and pyrolysis pipe, reduce carbon source and protect the dosage of nitrogen, the infiltration gas of acquisition is rich
Fuel of the hydrogen as preheating furnace, reduces the dosage of fuel gas.Due to fully and rationally using for tail gas each component, using lighter hydrocarbons
The carbon material preparation process of Catalytic Thermal Decomposition route, not only may be implemented near-zero release, but also cost can be significantly reduced.
Technical solution of the present invention:
A kind of near-zero release carbon material preparation process of UF membrane coupling lighter hydrocarbons thermal decomposition, described includes that UF membrane couples
Lighter hydrocarbons thermal decomposition near-zero release carbon material preparation process used in system include pyrolytic reaction pipe 1, heat exchanger 2, cooler 3,
Compressor 4, hydrogen film separation unit 5 and preheating furnace 6；
The lighter hydrocarbons Catalytic Thermal Decomposition tail gas S-1 being discharged from pyrolytic reaction pipe 1, is successively down to often through heat exchanger 2, cooler 3
Wen Hou improves pressure into compressor 4, enters back into operation temperature needed for heat exchanger 2 is preheated to hydrogen film separation unit 5；
Through compression and pretreated lighter hydrocarbons Catalytic Thermal Decomposition tail gas S-1, as the unstripped gas S-2 of hydrogen film separation unit 5,
Infiltration gas S-3 is obtained in the low-pressure side of hydrogen film separation unit 5, is rich in hydrogen；It is obtained in the high-pressure side of hydrogen film separation unit 5
Residual air S-4 is seeped, nitrogen and hydro carbons are rich in；
Infiltration gas S-3 rich in hydrogen, since nitrogen largely removes, combustion flame temperature is significantly improved, with normal combustion
Expect the combustion chamber for entering preheating furnace 6 after gas S-5 mixing, using air S-6 as combustion adjuvant, combustion heat supplying in a combustion chamber；
Infiltration residual air S-4 rich in nitrogen and hydro carbons, the accumulation of hydrogen is avoided by UF membrane, with normal gaseous carbon source S-
Enter preheating furnace 6 after 8 and inert nitrogen gas S-9 mixing is heated side, reaches thermal decomposition temperature and enters pyrolytic reaction later
Carbon material is generated in pipe 1.
Beneficial effects of the present invention: preparation process of the invention is by hydrogen membrane separation technique and lighter hydrocarbons Catalytic Thermal Decomposition device
Gaseous carbon source and diluent gas is greatly decreased in lighter hydrocarbons and nitrogen return preheating furnace and pyrolysis pipe in tail gas by coupling
Dosage, by fuel as preheating furnace after the hydrogen concentration for thermally decomposing by-product, the dosage of significant saving fuel gas.It is urged with propylene
For thermal decomposition process, the gaseous carbon source dosage of UF membrane coupling technique can reduce about 21.6%, and nitrogen use level can be reduced about
92.0%, fuel gas dosage can save 80% or more.Generally speaking, the carbon material preparation of UF membrane coupling lighter hydrocarbons Catalytic Thermal Decomposition
The near-zero release of production process not only may be implemented by fully and rationally using the lighter hydrocarbons in tail gas, nitrogen and hydrogen in technique,
Cost can also be significantly reduced.
Detailed description of the invention
Fig. 1 is the carbon material preparation principle process flow of UF membrane coupling lighter hydrocarbons Catalytic Thermal Decomposition.
In figure: 1 pyrolytic reaction pipe；2 heat exchangers；3 coolers；4 compressors；5 hydrogen film separation units；6 preheating furnaces；S-1
Lighter hydrocarbons Catalytic Thermal Decomposition tail gas；The unstripped gas of S-2 film separation unit；S-3 permeates gas；S-4 seeps residual air；The normal fuel gas of S-5；
S-6 air；S-7 combustion tail gas；S-8 gaseous carbon source；S-9 nitrogen.
Specific embodiment
With reference to the accompanying drawing and technical solution, a specific embodiment of the invention is further illustrated.
Embodiment 1
It in embodiment 1, is the Catalytic Thermal Decomposition carbon material preparation facilities of gaseous carbon source for propylene, using hydrogen membrane point
It is improved from technology.Unitary device produces about 90 tons of carbon material per year, consumes 12 side of marking of propylene, 30 side of marking of nitrogen, fuel per hour
11 side of marking of gas, about 60 mark side of by-product hydrogen containing tail gas.Tail gas composition: hydrogen about 48mol%；Nitrogen about 46mol%；Unreacted low-carbon
Hydro carbons includes the about 6mol% such as methane, ethylene, ethane, propylene and propane.Tail gas pressure is about 0.05MPaG.
Hydrogen membrane separation device handles the tail gas generated to the Catalytic Thermal Decomposition device of 12 operations simultaneously.Hydrogen
The performance parameter of seperation film: hydrogen/nitrogen is selectively 80；Hydrogen/methane selectively is 100；Hydrogen/Propylene Selectivity 107；
Hydrogen permeation rate is 200GPU.
Thermal decomposition tail gas be cooled to 40 DEG C after enter compressor, be pressurized to 1.80MPaG, be then preheated to 65~85 DEG C into
Enter film separation unit.The infiltration gas for being rich in hydrogen is obtained in low-pressure side, per hour about 360 mark side of output, composition: hydrogen
91.2mol%；Nitrogen 8.0mol%；Unreacted low-carbon hydro carbons 0.8mol%.The infiltration for being rich in nitrogen and hydro carbons is obtained in high-pressure side
Residual air, about 360 mark side of output, forms: hydrogen 5.0mol% per hour；Nitrogen 83.9mol%；Unreacted low-carbon hydro carbons
11.1mol%.
Compressor horsepower is about 100kW, and membrane area is about 400 square metres.Annual operating cost was by 6000 hours about 650,000
210,000 yuan of first depreciation, 440,000 yuan of public work.Using infiltration gas as fuel, about 108 mark side of fuel is saved per hour；Residual air will be seeped
It is recycled back to preheating furnace and pyrolytic reaction pipe, saves 31 side of marking of carbon source propylene, 331 side of marking of nitrogen per hour.The fuel of above-mentioned saving
Gas, propylene and nitrogen, total value are about 5,600,000 yuan/year.
Generally, thermal decomposition tail gas is fully and rationally used by membrane separation device, annual cost-saved about 4,950,000
Member.
Embodiment 2
It in example 2, is the Catalytic Thermal Decomposition carbon material preparation facilities of gaseous carbon source for ethylene, using hydrogen membrane point
It is improved from technology.Unitary device produces about 80 tons of carbon material per year, per hour 18 side of marking of consumption of ethylene, 36 side of marking of nitrogen, fuel
10 side of marking of gas, about 72 mark side of by-product hydrogen containing tail gas.Tail gas composition: hydrogen about 41mol%；Nitrogen about 50mol%；Unreacted low-carbon
Hydro carbons includes the about 9mol% such as methane, ethylene, ethane, propylene and propane.Tail gas pressure is about 0.05MPaG.
Hydrogen membrane separation device handles the tail gas generated to the Catalytic Thermal Decomposition device of 14 operations simultaneously.Hydrogen
The performance parameter of seperation film: hydrogen/nitrogen is selectively 120；Hydrogen/methane selectively is 150；Hydrogen/ethylene selectivity
155；Hydrogen permeation rate is 180GPU.
Thermal decomposition tail gas be cooled to 40 DEG C after enter compressor, be pressurized to 2.00MPaG, be then preheated to 65~85 DEG C into
Enter film separation unit.The infiltration gas for being rich in hydrogen is obtained in low-pressure side, per hour about 413 mark side of output, composition: hydrogen
92.8mol%；Nitrogen 6.3mol%；Unreacted low-carbon hydro carbons 0.9mol%.The infiltration for being rich in nitrogen and hydro carbons is obtained in high-pressure side
Residual air, about 595 mark side of output, forms: hydrogen 5.0mol% per hour；Nitrogen 80.4mol%；Unreacted low-carbon hydro carbons
14.6mol%.
Compressor horsepower is about 140kW, and membrane area is about 500 square metres.Annual operating cost was by 6000 hours about 940,000
320,000 yuan of first depreciation, 620,000 yuan of public work.Using infiltration gas as fuel, about 235 mark side of fuel is saved per hour；Residual air will be seeped
It is recycled back to preheating furnace and pyrolytic reaction pipe, saves 67 side of marking of carbon source ethylene, 478 side of marking of nitrogen per hour.The fuel of above-mentioned saving
Gas, ethylene and nitrogen, total value are about 10,160,000 yuan/year.
Generally, thermal decomposition tail gas is fully and rationally used by membrane separation device, annual cost-saved about 9,220,000 yuan.
Claims (1)
1. a kind of near-zero release carbon material preparation process of UF membrane coupling lighter hydrocarbons thermal decomposition, which is characterized in that described includes
System used in the near-zero release carbon material preparation process of UF membrane coupling lighter hydrocarbons thermal decomposition includes pyrolytic reaction pipe (1), heat exchange
Device (2), cooler (3), compressor (4), hydrogen film separation unit (5) and preheating furnace (6)；
The lighter hydrocarbons Catalytic Thermal Decomposition tail gas (S-1) being discharged from pyrolytic reaction pipe (1) is successively dropped through heat exchanger (2), cooler (3)
To room temperature, pressure is improved into compressor (4), enters back into behaviour needed for heat exchanger (2) is preheated to hydrogen film separation unit (5)
Make temperature；
Unstripped gas (S- through compression and pretreated lighter hydrocarbons Catalytic Thermal Decomposition tail gas (S-1), as hydrogen film separation unit (5)
2) infiltration gas (S-3), is obtained in the low-pressure side of hydrogen film separation unit (5), is rich in hydrogen；In hydrogen film separation unit (5)
High-pressure side, which obtains, seeps residual air (S-4), is rich in nitrogen and hydro carbons；
Infiltration gas S-3 rich in hydrogen, since nitrogen largely removes, combustion flame temperature is significantly improved, with normal fuel gas
(S-5) combustion chamber for entering preheating furnace (6) after mixing, with air (S-6) for combustion adjuvant, combustion heat supplying in a combustion chamber；
Infiltration residual air (S-4) rich in nitrogen and hydro carbons, the accumulation of hydrogen is avoided by UF membrane, with normal gaseous carbon source (S-
8) and after inert nitrogen gas (S-9) mixing enter preheating furnace (6) is heated side, reaches thermal decomposition temperature and enters pyrolysis later
Carbon material is generated in reaction tube (1).
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Cited By (2)
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| CN113357840A (en) * | 2021-06-03 | 2021-09-07 | 大连理工大学 | Low-temperature enhanced permselectivity nitrogen-containing natural gas membrane separation process |
| CN114478170A (en) * | 2022-02-23 | 2022-05-13 | 大连理工大学 | Membrane coupling polypropylene tail gas recovery process for reducing propane accumulation |
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Cited By (2)
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| CN114478170A (en) * | 2022-02-23 | 2022-05-13 | 大连理工大学 | Membrane coupling polypropylene tail gas recovery process for reducing propane accumulation |
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