CN109111935A - Oil shale recirculating fluidized bed method for destructive distillation and system based on methane rich gaseous mixture - Google Patents
Oil shale recirculating fluidized bed method for destructive distillation and system based on methane rich gaseous mixture Download PDFInfo
- Publication number
- CN109111935A CN109111935A CN201811061572.5A CN201811061572A CN109111935A CN 109111935 A CN109111935 A CN 109111935A CN 201811061572 A CN201811061572 A CN 201811061572A CN 109111935 A CN109111935 A CN 109111935A
- Authority
- CN
- China
- Prior art keywords
- destructive distillation
- gas
- oil shale
- oil
- gaseous mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
- C10B49/04—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated
- C10B49/08—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form
- C10B49/10—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form according to the "fluidised bed" technique
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/06—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
Abstract
The invention belongs to energy fields, more particularly to oil shale recirculating fluidized bed method for destructive distillation and system based on methane rich gaseous mixture, this method is using the activating mixed gas body of methane rich gaseous mixture and carbon dioxide as fluidizing gas, and the semicoke of oil shale fluidized retoring is taken up in order of priority heating catalyst layer with heat exchange method and heat exchange gas chamber promotes the catalytic activation of methane rich gaseous mixture and carbon dioxide；Except the fluidized retoring product of half afocal respectively obtains shale oil, fixed gas and water after gas solid separation, condensation liquefaction and water-oil separating, the solid particulate matter that gas solid separation goes out returns to destructive distillation room and further reacts, and improves oil shale retorting conversion ratio.The activating mixed gas of methane rich gaseous mixture and carbon dioxide can come into full contact with oil shale, be conducive to anakmetomeres in conjunction with oil shale retorting free radical, improve oil yield, reduce hydropyrolysis cost, reduce greenhouse gas emission, improve environment；Catalyst is easy to circular regeneration and reuse.And it is easy to operate, it is easy to be mass produced.
Description
Technical field
The invention belongs to energy fields, and in particular to the oil shale recirculating fluidized bed method for destructive distillation based on methane rich gaseous mixture
And system.
Background technique
Oil shale is a kind of rich reserves, widely distributed unconventional petroleum resources.Oil shale is as a kind of important energy
Source mineral resources can not only extract shale oil and related petrochemicals, also act as the combustion of power generation, heating and transport etc.
Material.Oil shale retorting method for producing oil mainly includes underground retoring method and ground cracking process, the former is also known as original place destructive distillation or in situ dry
It evaporates, refers to that subterranean oil shale is directly heated without exploitation and generate shale oil export ground, caused by easily being revealed to subterranean strata because of oil gas
Pollution and low oil yield, always non-industrialized production.After the latter refers to that oil shale recovery transports ground, pass through process units destructive distillation system
The method of oil.At present China carry out large-scale industrial production oil shale retorting technology based on the destructive distillation of ground (Li X.X.,
et al.Energy,2015,82:31-42.).Traditional retorting technique is mature, at low cost, process is simple, but in oil shale
Organic efficiency of carbon con version is low, and yield of the product is not high, at the same in shale oil containing the non-hydrocarbon compounds such as a large amount of sulfur-bearing, nitrogen and oxygen and
The aromatic hydrocarbons and alkene of high level, these compounds lead to the reduction of shale oil stability, and when burning discharges NOxAnd SOxDeng pollution
Object increases the problems such as oil refinery is difficult, and raising process complexity is with refining oil cost, and soda acid slag being brought to pollute.
The free radical that oil shale retorting generates is stablized in hydrotoring and catalytic hydrogenation destructive distillation by external hydrogen source, reduces freely
Polycondensation reaction between base improves organic efficiency of carbon con version, improves yield of the product to a certain extent, while removing in shale oil
The heteroatomic compounds such as sulfur-bearing, nitrogen and oxygen, carry out unsaturated materials plus hydrogen saturation, realization shale oil lighting improve shale
The stability (Dai F., et al.Fuel, 2016,166:19-23) of oil, but high hydrogen manufacturing cost and in-situ impregnation catalysis
The problems such as recycling of agent is difficult affects the industrialization of corresponding retorting technique.
Methane is the main component of natural gas, shale gas or oil shale pyrolysis gas, cheap, from a wealth of sources, H/C atom
It is ideal substitution hydrogen source than high.Methane there is no anti-when being lower than 800 DEG C with oil shale directly as reaction atmosphere
It answers, suitable with the effect of inert atmosphere, this is mainly that methane molecule chemical property is stablized, not easily-activated under low temperature.
Steinberg of Brookhaven National Laboratory et al. (Steinberg M., et al.St.Louis:American
Chemical society, 1984) section of U.S. sieve under three kinds of methane, hydrogen and helium atmosphere has been investigated on entrained-flow reactor
Draw the fast pyrogenation characteristic of heavy wool shale.The result shows that when reaction temperature is 800 DEG C, when pressure is 3.5MPa, under methane atmosphere
Organic efficiency of carbon con version highest, followed by hydrogen, minimum is helium.But the oil shale residence time is shorter in entrained-flow reactor,
It is unfavorable for oil shale particle sufficiently to decompose, while shale oil gas carrying solid impurity is more, increases separating difficulty, is also unfavorable for page
Shale oil subsequent processing." destructive distillation of oil shale bubbling bed and semicoke circulating fluidized bed combustion combined system (CN
Oil shale retorting, residence time of the oil shale in bubbling fluidized bed reactor 102295941B) " are carried out using bubbling fluidized bed
Extend, help to improve oil shale heat conversion, but the oil shale of the not completely dry fraction solution in part, which is mixed into semicoke, loses one
Divide oil product.
Under the action of catalyst, methane activation produces the free radical intermediates such as methyl, methylene.It is " a kind of to be rich in first
Alkane gaseous mixture is the method (CN 101747922A) that reaction atmosphere improves fluidized bed coal pyrolytic tar yield " open methane rich is mixed
Gas is closed after 850 DEG C of catalytic activations, the tar yield of pyrolytic reaction is carried out at 750 DEG C or 800 DEG C with coal, when being higher than mutually synthermal
Plus hydrogen or catalytic hydropyrolysis tar yield.Pyrolysis of coal semicoke is most of in the patent is directly arranged by side line in the middle part of fluidized bed
Enter semicoke storage tank, semicoke sensible heat is underused, the solids such as inabundant pyrolyzing coal, semicoke and catalyst that gaseous products carry
Grain is discharged after gas-solid separator separates, and leads to the waste for not being pyrolyzed coal resource sufficiently.
Minerals in coal content is lower than 40%, and oil shale mineral content is up to 50% or more, oil shale Minerals
Matter is closely linked with organic matter, during oil shale pyrolysis, these mineral absorption energy, and itself occur to divide
Solution interacts with organic matter, influences each other, and generates extreme influence to the pyrogenation and carbonization of organic matter in oil shale.Oil shale heat
Solution generates the temperature of shale oil no more than 600 DEG C, when temperature is more than 600 DEG C, the shale oil of generation two secondary fissure at high temperature
Solution reduces yield of the product.Therefore, whether oil shale is applicable in the shale oil extract under methane rich atmosphere, heat under methane rich atmosphere
Solution condition is how, the yield of the product under methane rich atmosphere how and methane rich atmosphere under use which kind of pyrogenation and carbonization device, both
Conducive to the abundant pyrogenation and carbonization of oil shale, and pyrolysis energy is made to be fully used, still required study.
Summary of the invention
The object of the present invention is to provide the oil shale recirculating fluidized bed method for destructive distillation based on methane rich gaseous mixture, this method benefits
In the abundant pyrogenation and carbonization of oil shale, shale oil quality and yield are improved, pyrolysis temperature is low, makes full use of pyrolysis energy, consumption temperature
Room gas, environment compatibility is strong, catalyst recyclable regenerative and reuse, and it is easy to operate, treating capacity is big, industrial applications
It has a extensive future.
The present invention also provides the oil shale recirculating fluidized bed distillation system based on methane rich gaseous mixture, the system is simple, closes
Reason, easy to operate, by the system, the abundant pyrogenation and carbonization of oil shale improves oil shale quality and yield, makes full use of pyrolysis energy
Amount.
The technical scheme is that the oil shale recirculating fluidized bed method for destructive distillation based on methane rich gaseous mixture, by following
Circulation fluidized bed reactor carries out fluidized retoring, and the structure of circulating fluid bed reactor includes destructive distillation room and heat exchange gas from top to bottom
Room, destructive distillation room bottom and heat exchange gas chamber junction are arranged catalyst layer, destructive distillation room include top dilute-phase zone and lower part it is close
Phase region；Step includes:
A. the fluidizing gas containing methane rich gaseous mixture and carbon dioxide enters recirculating fluidized bed after catalyst layer activates
The destructive distillation room of reactor, oil shale particle is under the activating mixed gas atmosphere of methane rich gaseous mixture and carbon dioxide, in recycle stream
The destructive distillation room of fluidized bed reactor carries out fluidized retoring；
B. the semicoke part generated is discharged and collects from destructive distillation room bottom；Air-flow carries remaining semicoke, its except half afocal
He is discharged destructive distillation product, non-dry rectificating oil shale and catalyst from the dilute-phase zone top of destructive distillation room；
C. after gas solid separation, semicoke, non-dry rectificating oil shale and catalyst return to the emulsion zone of destructive distillation room, remove half afocal
Other destructive distillation products condensation after, through water-oil separating, obtain shale oil and water.
Using the activating mixed gas of methane rich gaseous mixture and carbon dioxide as fluidizing gas, it is rich in hydrogen and methyl, Asia
The hydrogen-rich free radical such as methyl, hydrogen-rich free radical can be contacted with oil shale pyrolysis free radical, improve the steady of oil shale pyrolysis free radical
Constant speed rate and efficiency avoid the condensation between oil shale pyrolysis free radical, improve yield of the product；Hydrogen-rich free radical and hydrogen,
Can also make the objectionable impurities such as sulphur, oxygen, the nitrogen in shale oil be changed into hydrogen sulfide, water, ammonia and remove, and add alkene and alkadienes
Hydrogen saturation, aromatic moiety add hydrogen to be saturated, and aliphatic and aromatic hydrocarbons content increases in shale oil, and non-hydrocarbon compound content reduces, shale
Oily API is increased, and subsequent shale oil hydroprocessing processes are saved in oil product lighting.
Step a, under screw-feeder effect, oil shale particle is continuously pushed to destructive distillation in circulating fluid bed reactor
The emulsion zone of room.
Step a, the temperature of fluidized retoring are 400 DEG C~600 DEG C.Low temperature distillation is carried out at a temperature of the fluidized retoring, is protected
While demonstrate,proving organic matter pyrolysis generation shale oil in oil shale, shale oil second pyrolysis caused by high temperature is avoided.
The volume ratio of step a, methane rich gaseous mixture and carbon dioxide is 1:0.5~1.5, preferably 1:1.Carbon dioxide gas
While body promotes methane reforming hydrogen manufacturing, methyl hydride catalyzed activation can also be promoted to generate the hydrogen-rich free radicals such as methyl, methylene.
Step a, methane rich gaseous mixture are any one in natural gas, oil shale pyrolysis gas or shale gas or combination.When containing
When having that carbon dioxide content is lower in the fluidizing gas of methane rich gaseous mixture and carbon dioxide, oxygen can be also added into fluidizing gas
The volume ratio of the property changed gas, fluidizing gas and oxidizing gas is 1:0.3~1, preferably 1:0.5~0.6；Oxidizing gas is
Gaseous mixture, water vapour or air of carbon dioxide and oxygen etc. have any one or combination in oxidizing property gas, make first
The sufficiently catalytic oxidation of alkane.
Step a, catalyst is the loaded catalyst for making methane activation, including carrying transition metal, alkali in catalyst layer
The loaded catalyst of earth metal or alkali metal isoreactivity element, carrier be aluminum oxide, titanium dioxide, silica,
Magnesia or calcium oxide.Transition metal is any one in nickel, iron, copper or cobalt or combination.
Step b, the semicoke discharge line that the semicoke part of generation is arranged through destructive distillation room bottom, from top to bottom successively with catalysis
After oxidant layer and heat exchange gas chamber heat exchange, it is discharged and collects.
The semicoke sensible heat of oil shale pyrolysis destructive distillation is taken up in order of priority heating catalyst layer and heat exchange gas chamber with heat exchange method
The gaseous mixture of interior methane rich gaseous mixture and carbon dioxide, by semicoke sensible heat transfer urging to methane rich gaseous mixture and carbon dioxide
The catalytic activation gaseous mixture of change activating mixed gas, methane rich gaseous mixture and carbon dioxide enters destructive distillation room, and the heat of absorption is used
In oil shale fluidized retoring, partial heat is transferred again to semicoke, to catalyst layer and the indoor gas of heat exchange gas again into
Row heat exchange heating, the portion of energy of oil shale pyrolysis destructive distillation so recycle, avoid being largely lost and wasting for energy, subtract
Few outer supplying heat source, economizes on resources.
Oil shale recirculating fluidized bed distillation system based on methane rich gaseous mixture, including circulating fluid bed reactor, gas-solid
Separator, condenser and oil water separator are provided with heat exchange gas chamber, destructive distillation room and semicoke discharge in circulating fluid bed reactor
Pipeline, heat exchange gas chamber are located at below destructive distillation room and are connected to destructive distillation room；
Catalyst layer, the intersection setting of destructive distillation room and catalyst layer is arranged in destructive distillation room bottom and heat exchange gas chamber junction
There is first gas distribution grid, is connected to destructive distillation room and catalyst layer；The intersection of heat exchange gas chamber and catalyst layer is provided with second
Gas distribution grid is connected to heat exchange gas chamber and catalyst layer；Semicoke discharge line is connected to destructive distillation room bottom, and sequentially passes through
One gas distribution grid, catalyst layer, second gas distribution grid and heat exchange gas chamber；
The gaseous mixture of methane rich gaseous mixture, carbon dioxide or methane rich gaseous mixture and carbon dioxide enters from heat-exchanging chamber
Circulating fluid bed reactor；
Destructive distillation room includes the dilute-phase zone on top and the emulsion zone of lower part；
The entrance of gas-solid separator is connect with the top of destructive distillation room dilute-phase zone, and solid outlet is close by returning charge valve and destructive distillation room
The lower part of phase region is connected to, and gas vent connects condenser；
Condenser liquid outlet connects oil water separator.
Oil shale recirculating fluidized bed distillation system based on methane rich gaseous mixture is additionally provided with feed bin and screw-feeder, material
Storehouse is connected to the emulsion zone of destructive distillation room by screw-feeder.
For the reuse for realizing oil shale pyrolysis destructive distillation heat, reduces the loss and waste of energy to the greatest extent, economizes on resources,
Heat exchange gas chamber is set below destructive distillation room, and catalyst filling between destructive distillation room and heat exchange gas chamber is arranged in destructive distillation room bottom
Semicoke discharge line sequentially pass through catalyst layer and heat exchange gas chamber, and between destructive distillation room and catalyst layer, catalyst layer and heat
It is connected between exchange gas chamber, the semicoke sensible heat of oil shale pyrolysis destructive distillation is with the successive heating catalyst layer of heat exchange method and heat exchange
The gaseous mixture of gas indoor methane rich gaseous mixture and carbon dioxide ensures that the gaseous mixture of methane rich gaseous mixture and carbon dioxide is catalyzed
While activation, the activating mixed gas of methane rich gaseous mixture and carbon dioxide is transferred heat to；The methane rich for carrying heat is mixed
The activating mixed gas for closing gas and carbon dioxide enters destructive distillation room, will while providing heat and environment for oil shale pyrolysis destructive distillation
Partial heat is transferred again to semicoke, is recycled next time.
Circular regeneration and repetition to reduce pollution of the catalyst to oil shale retorting shale oil gas to the greatest extent, conducive to catalyst
It uses, first gas distribution grid is arranged in the intersection of catalyst layer and destructive distillation room, and the intersection of catalyst and heat exchange gas chamber is set
Second gas distribution grid is set, and combines the regulation to catalyst layer catalyst particle size, guarantees catalyst layer stability.
The invention has the advantages that:
(1) present invention carries out the pyrogenation and carbonization of oil shale using recirculating fluidized bed, and recirculating fluidized bed fluidizing gas velocity is low, extends
Oil shale is sufficiently pyrolyzed in the destructive distillation indoor residence time, for oil shale provides time guarantee；The returning charge of recirculating fluidized bed itself
Unreacted or not sufficiently reactive oil shale particle are returned to the dry of circulating fluid-bed by system (gas-solid separator and returning charge valve)
Evaporate room repeat pyrogenation and carbonization until oil shale be pyrolyzed completely, be sufficiently pyrolyzed for oil shale and number guarantee be provided；It improves according to this
Oil shale utilization rate and yield of the product, and the content of solid impurity in shale oil gas is reduced, improve the purity of shale oil.
(2) present invention is using the catalytic activation gaseous mixture of methane rich gaseous mixture and carbon dioxide as oil shale fluidized retoring
Fluidizing gas, in catalyst activation procedure, carbon dioxide promotes methane reforming hydrogen manufacturing, while improving hydrogen content, titanium dioxide
Carbon may additionally facilitate methane activation and generate the hydrogen-rich free radical intermediates such as methyl, methylene；Hydrogen and hydrogen-rich free radical improve shale
Oil yield, makes shale oil oil product lighting, and the objectionable impurities such as removal shale oil mineral improve shale oil purity；Compared to
Add hydrogen or catalytic hydropyrolysis, can also reduce pyrogenation and carbonization cost.
(3) while the method for the present invention and device guarantee oil shale abundant pyrogenation and carbonization, without being fluidized at high temperature
Destructive distillation avoids the second pyrolysis under shale oil high temperature, improves oil shale yield, energy saving, reduces input cost；And it is more applicable
The pyrogenation and carbonization of oil shale small in partial size, inferior.
(4) present invention makes full use of carbon dioxide, reduces greenhouse gas emission, reduces greenhouse effects, environmental-friendly, application
It has a extensive future.
Detailed description of the invention
Fig. 1 is the oil shale recirculating fluidized bed distillation system schematic diagram the present invention is based on methane rich gaseous mixture.
In figure: 1- feed bin；2- screw-feeder；3- circulating fluid bed reactor, 31- heat exchange gas chamber, 32- destructive distillation room,
321- emulsion zone, 322- dilute-phase zone；4- first gas distribution grid；5- catalyst layer；6- second gas distribution grid；The discharge of 7- semicoke
Pipeline；8- gas-solid separator；9- returning charge valve；10- condenser；11- oil water separator；12- wet flow indicator.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
The present invention is based on the oil shale recirculating fluidized bed distillation system of methane rich gaseous mixture as shown in Figure 1, include feed bin 1,
Screw-feeder 2, circulating fluid bed reactor 3, gas-solid separator 8, returning charge valve 9, condenser 10 and oil water separator 11, feed bin
Oil shale in 1 pushes to circulating fluid bed reactor 3 through screw-feeder 2, carries out pyrogenation and carbonization reaction；Recirculating fluidized bed is anti-
Device 3 is answered to be connected to gas-solid separator 8, gas-solid separator 8 is connected to condenser 10, and condenser 10 is connected to oil water separator 11.
Circulating fluid bed reactor 3 includes heat exchange gas chamber 31, destructive distillation room 32 and semicoke discharge line 7, heat exchange gas chamber
31 are located at 32 lower section of destructive distillation room and are connected to destructive distillation room 32, and destructive distillation room 32 includes positioned at the emulsion zone 321 of lower part and positioned at top
Dilute-phase zone 322.Oil shale in feed bin 1 pushes to the close of destructive distillation room 32 in circulating fluid bed reactor 3 through screw-feeder 2
Phase region 321 carries out fluidized retoring under the activating mixed gas atmosphere of methane rich gaseous mixture and carbon dioxide.31 He of heat exchange gas chamber
Catalyst layer 5 is provided between destructive distillation room 32, destructive distillation room 32 and the intersection of catalyst layer 5 are provided with first gas distribution grid 4,
It is connected to destructive distillation room 32 and catalyst layer 5；The intersection of heat exchange gas chamber 31 and catalyst layer 5 is provided with second gas distribution grid 6,
It is connected to heat exchange gas chamber 31 and catalyst layer 5；First gas distribution grid 4 and second gas distribution grid 6 are fixed, catalyst layer is isolated
Catalyst in 5 avoids catalyst to enter pollution shale oil gas in destructive distillation room 32 with air-flow as far as possible, and cooperates and urge in catalyst layer 5
Agent adjusts direction and the distribution of air-flow；Semicoke discharge line 7 setting is connected in 32 bottom of destructive distillation room with destructive distillation room 32, from up to
Under sequentially pass through first gas distribution grid 4, catalyst layer 5, second gas distribution grid 6 and heat exchange gas chamber 31, will be in destructive distillation room
The semicoke that oil shale retorting generates is discharged and collects.
Catalyst layer 5 is heated while semicoke is discharged from semicoke discharge line 7, is methane rich gaseous mixture and carbon dioxide
Catalytic activation of the gaseous mixture in catalyst layer 5 temperature guarantee is provided；It simultaneously can also be hot with entering in heat exchange gas chamber 31
It exchanges the methane rich gaseous mixture of gas chamber 31 and the gaseous mixture of carbon dioxide carries out reverse heat and exchanges, the methane rich after facilitating heating is mixed
The gaseous mixture for closing gas and carbon dioxide enters progress catalytic activation in catalyst layer 5；Methane rich gaseous mixture and carbon dioxide it is mixed
Gas is closed out of, heat exchange gas chamber 31 enters circulating fluid bed reactor 3 after 5 catalytic activation of catalyst layer destructive distillation room 32, for oil
Shale fluidized retoring provides heat, keeps oil shale fluidization dry in the activating mixed gas atmosphere of methane rich gaseous mixture and carbon dioxide
It evaporates.The high-temperature semi-coke that oil shale pyrolysis generates carries out heat exchange through catalyst layer 5 and heat exchange gas chamber 31 with semicoke discharge line 7
Collection is then exhausted from after cooling, under the catalytic activation and activation methane rich atmosphere of methane rich gaseous mixture and the gaseous mixture of carbon dioxide
Oil shale pyrolysis heat is provided, by the semicoke of oil shale fluidized retoring with the gaseous mixture of methane rich gaseous mixture and carbon dioxide
Between heat exchange, methane rich gaseous mixture and carbon dioxide gaseous mixture with the heat exchange between oil shale, realize oil shale stream
Change recycling for destructive distillation heat, reduces the loss and waste of energy to the greatest extent.
Circulating fluid bed reactor 3 is located at entering for the outlet gas-solid separator 8 on 322 top of dilute-phase zone of destructive distillation room 32
Mouthful, the fraction of unreacted oil of the destructive distillation product in addition to semicoke and the carrying of fluidized state downstream that oil shale retorting generates
Shale, semicoke and catalyst enter gas-solid separator 8 with air-flow；Gas-solid separator 8 is located at the solid outlet connection returning charge of lower part
Valve 9, returning charge valve 9 is connected to the lower part of the emulsion zone 321 of destructive distillation room 32, under the centrifugation of gas-solid separator 8, with air-flow into
Enter the solid particles such as non-dry rectificating oil shale, semicoke and the catalyst of gas-solid separator 8 to separate from gas, and through returning charge valve
9 return to the emulsion zone 321 of destructive distillation room 32, and non-dry rectificating oil shale re-starts dry distillation reactor, improve oil-shale retorting conversion ratio
And yield of the product；The superposed gas vent of gas-solid separator 8 is connected to the entrance of condenser 10, divides through gas-solid separator 8
Condenser 10, which is sent into, with gas from the destructive distillation product after purification in addition to semicoke carries out condensation liquefaction.Pass through gas-solid separator 8
The a little unreacted oil shale, semicoke and catalyst that are mingled in gas are separated and are removed by centrifugation, purifying oil shale fluidisation
Destructive distillation generate remove half afocal destructive distillation product, reduce solid impurity pollute, improve the quality of subsequent shale oil.
Condenser 10 is located at the liquid outlet connection oil water separator 11 of lower part, the superposed gas vent of condenser 10
Be provided with wet flow indicator 12, carry the gas for removing half afocal destructive distillation product in condenser 10, the liquid that condensation liquefaction generates into
Enter oil water separator 11 and carry out water-oil separating, obtains shale oil and water；Uncooled liquefied fixed gas is united through wet flow indicator 12
It is collected again after meter.
Use the oil shale recirculating fluidized bed destructive distillation system of the gaseous mixture based on methane rich gaseous mixture and carbon dioxide shown in Fig. 1
The process that system carries out oil shale retorting is as follows: the 0~20mm oil shale particle being stored in feed bin 1 is conveyed through screw-feeder 2
To the emulsion zone 321 of the destructive distillation room 32 of circulating fluid bed reactor 3, in the activating mixed gas of methane rich gaseous mixture and carbon dioxide
The fluidization destructive distillation of atmosphere, pyrolysis temperature are controlled at 400 DEG C~600 DEG C；The semicoke that oil shale fluidized retoring generates passes through and destructive distillation room
The semicoke purging line 7 of 32 connections is discharged and collects, the destructive distillation product except half afocal of oil shale fluidized retoring generation, non-destructive distillation
Oil shale, semicoke and catalyst enter the gas-solid separator 8 being connected to the dilute-phase zone 322 of destructive distillation room 32 with air-flow；
Rich in free radical intermediates such as methyl, methylene in the activating mixed gas of methane rich gaseous mixture and carbon dioxide, and
Hydrogen content is improved, the hydrogen-rich such as methyl, methylene free radical intermediate inhibits oil shale certainly in conjunction with oil shale pyrolysis free radical
By being mutually condensed between base, while improving yield of the product, hydrogen-rich free radical and hydrogen make sulphur, oxygen, nitrogen in shale oil etc.
Objectionable impurities be changed into corresponding hydrogen sulfide, water, ammonia and remove, and make that alkene and diene hydrogenation are saturated, aromatic moiety adds hydrogen
Saturation improves aliphatic and aromatic hydrocarbons content in shale oil, reduces non-hydrocarbon compound content, increases shale oil API, oil product lightweight
Change, reduces hydrogenation of shale oil treatment process；
Under the centrifugation of gas-solid separator 8, with air-flow enter the non-dry rectificating oil shale of gas-solid separator 8, semicoke and
The solid particles such as catalyst are separated from gas, and the returning charge valve 9 through being connected to gas-solid separator 8 returns to destructive distillation room 32
Emulsion zone 321, non-dry rectificating oil shale re-start dry distillation reactor, and semicoke passes through 7 row of semicoke discharge line being connected to destructive distillation room 32
Out and collect；Except the destructive distillation product of half afocal enters the condenser 10 being connected to gas-solid separator 8 with gas；
Under the effect of 10 condensation liquefaction of condenser, the destructive distillation that the carrying of condenser 10 removes half afocal is entered by gas-solid separator 8
The gas-condensate liquid metaplasia of product at condensate liquid enter the oil water separator 11 that be connected to condenser 10, progress water-oil separating,
Obtain shale oil and water；Uncooled liquefied fixed gas is collected after the statistics of wet flow indicator 12.
The semicoke that oil shale fluidized retoring generates in destructive distillation room 32 is handed over by semicoke discharge line 7 into 5 heat of catalyst layer
Cooling is changed, the reverse heat exchange of gaseous mixture for entering back into heat exchange gas chamber 31 and methane rich gaseous mixture and carbon dioxide is cooling, discharge
And while collection；The gaseous mixture of methane rich gaseous mixture and carbon dioxide adds through heat exchange gas chamber 31 and the reverse heat exchange of semicoke
Heat enters back into the activating mixed gas that destructive distillation room 32 forms methane rich gaseous mixture and carbon dioxide into 5 catalytic activation of catalyst layer
Atmosphere.
The volume ratio of methane rich gaseous mixture and carbon dioxide is 1:0.5~1.5, and methane rich gaseous mixture is natural gas, oily page
Any one in rock pyrolysis gas or shale gas or combination.When carbon dioxide contains in the gaseous mixture of methane rich gaseous mixture and carbon dioxide
When measuring lower, the gas that gaseous mixture, water vapour or air of carbon dioxide and oxygen etc. has oxidizing property can be also added, first is made
The sufficiently catalytic oxidation of alkane.This method efficiently uses greenhouse gases, slows down greenhouse effects, improves environment.
Catalyst is the loaded catalyst for making methane activation in catalyst layer 5, specially carrying transition metal, alkaline earth gold
Belong to or the loaded catalyst of alkali metal isoreactivity element, carrier are aluminum oxide, titanium dioxide, silica, oxidation
Magnesium or calcium oxide, it is preferable to use nickel, iron, copper or cobalts for transition metal.Above-mentioned catalyst have environmental protection, be easy to get, preparation cost is low etc.
Advantage.
Claims (10)
1. the oil shale recirculating fluidized bed method for destructive distillation based on methane rich gaseous mixture, which is characterized in that anti-by recirculating fluidized bed
Device (3) are answered to carry out fluidized retoring, the structure of circulating fluid bed reactor (3) includes destructive distillation room (32) and heat exchange gas from top to bottom
Room (31), destructive distillation room (32) bottom and heat exchange gas chamber (31) junction setting catalyst layer (5), destructive distillation room (32) include top
Dilute-phase zone (322) and lower part emulsion zone (321)；Step includes:
A. it is anti-that the fluidizing gas containing methane rich gaseous mixture and carbon dioxide enters recirculating fluidized bed after catalyst layer (5) activation
The destructive distillation room (32) of device (3) is answered, oil shale particle is following under the activating mixed gas atmosphere of methane rich gaseous mixture and carbon dioxide
The destructive distillation room (32) of circulation fluidized bed reactor (3) carries out fluidized retoring；
B. the semicoke part generated is discharged and collects from destructive distillation room (32) bottom；Air-flow carries remaining semicoke, its except half afocal
He is discharged destructive distillation product, non-dry rectificating oil shale and catalyst from dilute-phase zone (322) top of destructive distillation room (32)；
C. after gas solid separation, semicoke, non-dry rectificating oil shale and catalyst return to the emulsion zone (321) of destructive distillation room (32), remove
After other destructive distillation products condensation of half afocal, through water-oil separating, shale oil and water are obtained.
2. oil shale recirculating fluidized bed method for destructive distillation according to claim 1, which is characterized in that step a is fed in spiral
Under device effect, oil shale particle is continuously pushed to the emulsion zone (321) of the interior destructive distillation room (32) of circulating fluid bed reactor (3).
3. oil shale recirculating fluidized bed method for destructive distillation according to claim 1, which is characterized in that step a, fluidized retoring
Temperature is 400 DEG C~600 DEG C.
4. oil shale recirculating fluidized bed method for destructive distillation according to claim 1, which is characterized in that step a, methane rich mixing
The volume ratio of gas and carbon dioxide is 1:0.5~1.5.
5. oil shale recirculating fluidized bed method for destructive distillation according to claim 1, which is characterized in that step a, methane rich mixing
Gas is natural gas, oil shale pyrolysis gas or shale gas.
6. oil shale recirculating fluidized bed method for destructive distillation according to claim 1, which is characterized in that step a, in fluidizing gas
The volume ratio of addition oxidizing gas, fluidizing gas and oxidizing gas is 1:0.3~1, and oxidizing gas includes carbon dioxide
With any one or the combination in the gaseous mixture, water vapour or air of oxygen.
7. oil shale recirculating fluidized bed method for destructive distillation according to claim 1, which is characterized in that step a, catalyst layer
(5) interior catalyst is the loaded catalyst for making methane activation, the load including carrying transition metal, alkaline-earth metal or alkali metal
Type catalyst, carrier are aluminum oxide, titanium dioxide, silica, magnesia or calcium oxide.
8. oil shale recirculating fluidized bed method for destructive distillation according to claim 1, which is characterized in that step b, the semicoke of generation
Part through destructive distillation room (32) bottom be arranged semicoke discharge line (7), from top to bottom successively same catalyst layer (5) and enter heat hand over
After the gas heat exchange of air-exchanging chamber (31), it is discharged and collects.
9. the oil shale recirculating fluidized bed distillation system based on methane rich gaseous mixture, for realizing any one of claim 1~8 institute
The oil shale recirculating fluidized bed method for destructive distillation stated, which is characterized in that structure includes circulating fluid bed reactor (3), gas solid separation
Device (8), condenser (10) and oil water separator (11), circulating fluid bed reactor (3) is interior to be provided with heat exchange gas chamber (31), does
Room (32) and semicoke discharge line (7) are evaporated, heat exchange gas chamber (31) is located at below destructive distillation room (32) and is connected to destructive distillation room (32)；
Destructive distillation room (32) bottom and heat exchange gas chamber (31) junction setting catalyst layer (5), destructive distillation room (32) and catalyst layer
(5) intersection is provided with first gas distribution grid (4), connection destructive distillation room (32) and catalyst layer (5)；Heat exchange gas chamber (31)
It is provided with second gas distribution grid (6) with the intersection of catalyst layer (5), connection heat exchange gas chamber (31) and catalyst layer (5)；
Semicoke discharge line (7) is connected to destructive distillation room (32) bottom, and sequentially pass through first gas distribution grid (4), catalyst layer (5),
Second gas distribution grid (6) and heat exchange gas chamber (31)；
The gaseous mixture of methane rich gaseous mixture, carbon dioxide or methane rich gaseous mixture and carbon dioxide enters from heat-exchanging chamber (31)
Circulating fluid bed reactor (3)；
Destructive distillation room (32) includes the dilute-phase zone (322) on top and the emulsion zone (321) of lower part；
The entrance of gas-solid separator (8) is connect with the top of destructive distillation room (32) dilute-phase zone (322), and solid outlet passes through returning charge valve
(9) it is connected to the lower part of destructive distillation room (32) emulsion zone (321), gas vent connects condenser (10)；
Condenser (10) liquid outlet connects oil water separator (11).
10. the oil shale recirculating fluidized bed distillation system according to claim 9 based on methane rich gaseous mixture, feature exist
In further including feed bin (1) and screw-feeder (2), feed bin (1) is connected to the close of destructive distillation room (32) by screw-feeder (2)
Phase region (321).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811061572.5A CN109111935B (en) | 2018-09-12 | 2018-09-12 | Oil shale circulating fluidized bed dry distillation method and system based on methane-rich mixed gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811061572.5A CN109111935B (en) | 2018-09-12 | 2018-09-12 | Oil shale circulating fluidized bed dry distillation method and system based on methane-rich mixed gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109111935A true CN109111935A (en) | 2019-01-01 |
| CN109111935B CN109111935B (en) | 2020-07-17 |
Family
ID=64859313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811061572.5A Active CN109111935B (en) | 2018-09-12 | 2018-09-12 | Oil shale circulating fluidized bed dry distillation method and system based on methane-rich mixed gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109111935B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170328A (en) * | 2020-02-07 | 2020-05-19 | 中国科学院兰州化学物理研究所 | Method for improving oil shale semicoke whiteness through composite titanium dioxide |
| CN112453018A (en) * | 2020-10-29 | 2021-03-09 | 上海工程技术大学 | Wet garbage poly-generation comprehensive utilization system and process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB749222A (en) * | 1953-05-15 | 1956-05-23 | Bataafsche Petroleum | Process and apparatus for effecting vapour-phase reactions with finely divided solid catalysts |
| CN101747922A (en) * | 2010-01-05 | 2010-06-23 | 大连理工大学 | Method for increasing yield of coal-pyrolysis-based tar in reaction atmosphere of methane-rich gas mixture in fluidized bed |
| US20110005976A1 (en) * | 2007-06-14 | 2011-01-13 | Eni S.P.A. | Enhanced process for the hydroconversion of heavy oils through ebullated-bed systems |
-
2018
- 2018-09-12 CN CN201811061572.5A patent/CN109111935B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB749222A (en) * | 1953-05-15 | 1956-05-23 | Bataafsche Petroleum | Process and apparatus for effecting vapour-phase reactions with finely divided solid catalysts |
| US20110005976A1 (en) * | 2007-06-14 | 2011-01-13 | Eni S.P.A. | Enhanced process for the hydroconversion of heavy oils through ebullated-bed systems |
| CN101747922A (en) * | 2010-01-05 | 2010-06-23 | 大连理工大学 | Method for increasing yield of coal-pyrolysis-based tar in reaction atmosphere of methane-rich gas mixture in fluidized bed |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170328A (en) * | 2020-02-07 | 2020-05-19 | 中国科学院兰州化学物理研究所 | Method for improving oil shale semicoke whiteness through composite titanium dioxide |
| CN112453018A (en) * | 2020-10-29 | 2021-03-09 | 上海工程技术大学 | Wet garbage poly-generation comprehensive utilization system and process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109111935B (en) | 2020-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102465043B (en) | Multi-section fractional pyrolysis gasification device and method for solid fuel | |
| CN101555420B (en) | Method, system and equipment for catalytic coal gasification | |
| CN104232147B (en) | A kind of heavy oil lightweight treatment technique | |
| CN102849676B (en) | High-temperature water vapor pyrolysis-cracking-gasification device and method for solid fuel | |
| CN102060662B (en) | Chemical power poly-generation energy system and method for recycling CO2 | |
| CN102198934A (en) | Method and device for producing hydrogen by using chemical chain | |
| CN102010759A (en) | Method and device for producing hydrogen-rich gases by catalyzing and gasifying solid fuels | |
| CN102585947A (en) | Method and device for preparing methane-containing gas by using coal | |
| CN108531220A (en) | A kind of system and method for biomass microwave pyrolysis high yield gas | |
| CN104098419B (en) | Coal, natural gas combination preparing light olefins from methanol system and method | |
| CN109111935A (en) | Oil shale recirculating fluidized bed method for destructive distillation and system based on methane rich gaseous mixture | |
| CN102234535B (en) | Method for processing low-quality heavy oil and simultaneously producing synthetic gas | |
| CN104945215B (en) | Method and system for preparing ethylene from powdered coal | |
| CN102559226A (en) | Coal pyrolysis system and pyrolysis method | |
| CN104046373A (en) | Method for preparing bio-oil and synthesis gas from biomass | |
| CN212800244U (en) | Chemical integrated system based on rich oil coal gas co-production technology | |
| CN204981692U (en) | System for fine coal preparation ethylene | |
| CN107163989A (en) | A kind of high temperature contains tar/hydrocarbon raw material gas methanation process | |
| CN104725181B (en) | Initial separation technique of gas generated by reaction for preparing propylene from oxygen-containing compounds | |
| CN203999432U (en) | Coal, Sweet natural gas coupling preparing light olefins from methanol system | |
| CN209428459U (en) | A kind of fine coal comprehensive utilization device | |
| CN209292290U (en) | A kind of oil-sand and greasy filth comprehensive utilization device | |
| CN113337317A (en) | Method for preparing biodiesel by indirect liquefaction of biomass | |
| CN108456127B (en) | Method for preparing low-carbon olefin by multistage catalytic cracking of biomass | |
| CN206089606U (en) | Gaseous replacement coke oven gas preparation liquefied natural gas's device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |