CN106701142B - The device and method that fuel is produced in catalysis pyrolysis are blended in high and low effective hydrogen-carbon ratio raw material - Google Patents
The device and method that fuel is produced in catalysis pyrolysis are blended in high and low effective hydrogen-carbon ratio raw material Download PDFInfo
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- CN106701142B CN106701142B CN201710052585.5A CN201710052585A CN106701142B CN 106701142 B CN106701142 B CN 106701142B CN 201710052585 A CN201710052585 A CN 201710052585A CN 106701142 B CN106701142 B CN 106701142B
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/02—Combustion or pyrolysis
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- Life Sciences & Earth Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of high and low effective hydrogen-carbon ratio raw materials, and the device and method that fuel is produced in catalysis pyrolysis are blended, which includes premixed device, two-stage screw feeder, motor, feed bin, fluidized bed pyrolyzer, cyclone separator, condensed in two stages device, coke bin, oil storage tank, air accumulator, preheater.The different material of high and low effective hydrogen-carbon ratio can be blended by this method using the device is catalyzed pyrolysis.The present invention can convert the low carbonaceous solids waste Cheap highly effective of effective hydrogen-carbon ratio in the liquid fuel of high-quality, handle the solid waste such as the high plastics of effective hydrogen-carbon ratio simultaneously, it solves the effectively carbonaceous solids waste such as low biomass of hydrogen-carbon ratio at present and converts difficulty, thermal decomposition product quality is not high, poor selectivity, the fast problem of the easy coking of catalyst, inactivation.
Description
Technical field
The invention belongs to solid waste conversion preparing liquid fuel and technical field of chemical products, and in particular to a kind of
The device and method that fuel is produced in catalysis pyrolysis are blended in high and low effective hydrogen-carbon ratio raw material.
Background technology
Alkene and aromatic hydrocarbon play very important as most basic Organic Chemicals in modern petroleum and chemical industry
Effect.Especially monocycle benzene class and low-carbon alkene are the flagship products of petrochemical industry.But with the worsening shortages of petroleum resources
With crisis, China is faced with stern challenge in terms of the energy and chemical industry.Therefore seek a kind of regenerative resource to realize pair
The replacement of petroleum-based feedstock is extremely urgent.
In regenerative resource, biomass is only origin of organic carbon, can be generated by way of being catalyzed and being pyrolyzed more
Alkene and aromatic hydrocarbon, realize to the partial alternative of petroleum-based feedstock, receive the attention of various circles of society in recent years.With fossil energy
It compares, biomass energy has the characteristics that recyclability, is distributed wide, low stain, and China is as a large agricultural country, biomass resource
Abundant, the biomass energy that can be developed and used every year at present is about 9.3 hundred million tons of standard coals.But the utilization rate of biomass energy is very
It is low, less than the 1% of China's using energy source total amount, therefore biomass energy is developed and used with huge potentiality.
It is a kind of more promising conversion technology of biomass energy that biomass, which is directly catalyzed pyrolysis, but biomass itself is relatively low
Hydrogen content be restrict its catalytic conversion efficiency this quality factor.And during the reaction, catalyst easily inactivates, and causes mesh
Mark the reduction of products collection efficiency.The reactions such as dehydration, decarbonylation base and decarboxylation life occurs in pyrolytic process for biomass and its derivative
At intermediate OXO products, multi-methyl benzene active intermediate is formed under the action of active site in catalyst duct.Reactant exists
It is catalytically conveted to alkene and aromatic hydrocarbon on multi-methyl benzene branch.The transfer for relying primarily on hydrogen realizes that raw material turns to target product
Change.Meanwhile the dehydrogenation of reactant or arene compound makes their polymerization cokings.Therefore, the content of hydrogen is higher in raw material,
The case where conversion ratio to target product is higher, and the relative amount of carbon is lower in raw material, catalyst coking is lighter.
The definition of effective hydrogen-carbon ratio is formula (1), and wherein C, H, O, N and S is respectively its mole.
Effective hydrogen-carbon ratio is higher, it is meant that the opposite hydrogen content of biomass material is higher, and carbon content is lower.Biomass catalyzing
The conversion ratio of conversion is higher, and catalyst coking is fewer.And when effective hydrogen-carbon ratio of biomass charging is less than 1, in reaction process
In be difficult to convert the feedstock to the petrochemical industry class product of high-quality by zeolitic catalyst ZSM-5, this is mainly due to catalysis
The rapid deactivation of agent.However effective hydrogen-carbon ratio of biomass is only 0-0.3.Therefore, the effective hydrogen-carbon ratio for improving raw material, from reaction
Source solve the problems, such as " hydrogen source ".The phenomenon that alleviating catalyst coking and deactivation is not only facilitated in this way, but also can improve production
The selectivity of the chemicals such as the yield of hydrocarbon and alkene, aromatic hydrocarbon in object.
Plastics are relatively close to as a kind of daily life rubbish, and with biomass pyrolytic temperature, are a kind of more satisfactory
It is catalyzed pyrolysis feed altogether.Plastics and the copyrolysis of biomass have to act synergistically well, high condensate of the plastics as alkene,
Depolymerization reaction can occur in pyrolytic process, generate the alkene of oligomerization.The alkene of oligomerization not only can be with initial ring itself
Change reaction and generate aromatic compound, but also can carry out reacting with biomass derivatives and generate aromatic hydrocarbon.Therefore, with life
Substance is the mixed catalytic of low effective hydrogen-carbon ratio raw material of representative and the height effectively hydrogen-carbon ratio raw material by representative of vinyon
Pyrolysis, can make full use of biomass and waste plastics resource, obtain the alkene and aromatic hydrocarbon of high yield, be biomass and waste plastics
Using an effective way is provided, this is of great significance to the present situation for solving China's oil shortage of resources.
Invention content
Goal of the invention：In order to overcome the deficiencies in the prior art, it is former that the present invention provides a kind of high and low effective hydrogen-carbon ratio
Material is blended catalysis pyrolysis and produces the device of fuel, while additionally providing total using the high and low effective hydrogen-carbon ratio raw material of device progress
The method that fuel is produced in mixed catalysis pyrolysis, it is difficult to solve effective hydrogen-carbon ratio raw material conversion low at present, thermal decomposition product quality is high,
Poor selectivity, the fast problem of the easy coking of catalyst, inactivation.
Technical solution：To achieve the above object, the technical solution adopted by the present invention is：
The device of fuel, including premixed device, level-one horse are produced in a kind of high and low effective hydrogen-carbon ratio raw material blending catalysis pyrolysis
It reaches, two level motor, feed bin, level-one feeding screw, deuterostrophies feeder, fluidized bed pyrolyzer, cyclone separator, coke
Storehouse, level-one condensing unit, B grade condensing unit, oil storage tank and air accumulator；
The outlet of the premixed device is connected with the entrance of feed bin, and the outlet of feed bin is located at the entrance of level-one feeding screw
Place, level-one feeding screw connect with level-one motors, by level-one motor driving level-one feeding screw, deuterostrophies into
The entrance of glassware is located at the exit of level-one feeding screw, the outlet of deuterostrophies feeder and the entrance of fluidized bed pyrolyzer
It is connected, deuterostrophies feeder is connected with two level motors, and deuterostrophies feeder is driven by two level motor；
The entrance of the upper gas outlet connection cyclone separator of the fluidized bed pyrolyzer, the gas phase of cyclone separator go out
Mouth is connected with the entrance of level-one condensing unit, and the solid-phase outlet of cyclone separator is connected with the entrance of coke bin；
The gas vent of the level-one condensing unit is connected with the entrance of B grade condensing unit, the gas of B grade condensing unit
Outlet is connected with air accumulator entrance, and reservoir outlet is connected with the bottom carrier gas inlet of fluidized bed pyrolyzer；After reaction one
In grade condensing unit, B grade condensing unit in the liquids recovery to oil storage tank of condensation.
Preferably, the level-one feeding screw and deuterostrophies feeder constitute two-stage screw feeding mechanism, and feed bin is logical
Two-stage screw feeding mechanism and fluidized bed pyrolyzer indirect communication are crossed, prevents the carrier gas in fluidized bed pyrolyzer from playing a reversed role into feed bin；
In order to ensure feed bin not back-mixing, nitrogen is passed through in feed bin as feed bin gas, the flow of feed bin gas is to be flowed in fluidized bed pyrolyzer
Change the 30%~50% of throughput.
Preferably, the level-one condensing unit (10) is made of test tube and cylinder body, in vitro injects deionized water, test tube
Between be connected to by emulsion tube, mixture of ice and water is held in cylinder body, test tube is immersed in the mixture of ice and water in cylinder body, makes test tube
The temperature of interior deionized water is maintained within the scope of 0~2 DEG C；The B grade condensing unit (11) is made of test tube and cylinder body, is trying
Ice ethyl alcohol is injected in pipe, is connected to by emulsion tube between test tube, dry ice is held in cylinder body, test tube is immersed in the dry ice in cylinder body
In so that the temperature of ice ethyl alcohol is maintained within the scope of -40~-45 DEG C in test tube.
Preferably, the air distribution plate of the fluidized bed pyrolyzer (7) is made of stainless steel cloth, and mesh diameter is 300 mesh；Stream
It is nitrogen or the non-condensation gas that pyrolysis generates to change the carrier gas in bed pyrolysis apparatus (7), and bed material is selected catalyst.
Preferably, deuterostrophies feeder (6) duration of runs is twice of level-one feeding screw (5), to ensure
The raw material that level-one feeding screw (5) is conveyed is completely into the fluidized bed pyrolyzer (7).
A method of high and low effective hydrogen-carbon ratio raw material based on above-mentioned apparatus is blended catalysis pyrolysis and produces fuel, including
Following steps：
(1) high and low effective hydrogen-carbon ratio raw material is blended：High effectively hydrogen-carbon ratio raw material, low effective hydrogen-carbon ratio raw material are being premixed
Be mixed and fed into feed bin in device, opening feed bin gas auxiliary and feeding simultaneously prevents back-mixing, the mixed raw material in feed bin through level-one spiral into
The screw rod of glassware and deuterostrophies feeder is forced into fluidized bed pyrolyzer；
(2) catalysis pyrolysis is blended in high and low effective hydrogen-carbon ratio raw material：High and low effective hydrogen-carbon ratio raw material is being fluidized with catalyst
Catalytic pyrolysis reaction occurs in bed pyrolysis apparatus, hydrogen migration occurs, product enters cyclone separator, into promoting the circulation of qi in cyclone separator
Solid phase detaches, and solid product is the catalyst inactivated and the charcoal particle for reacting generation after reaction, and into coke bin, gas-phase product is
It is pyrolyzed the volatile matter generated, into level-one condensing unit；
(3) high-quality liquid fuel is produced in condensation：Biomass pyrolytic gas phase product passes through level-one condensing unit, and boiling point is 0
DEG C or more ingredient condensation stay in test tube, boiling point 0 DEG C of ingredient below it is uncooled enter B grade condensing unit, B-grade condensation
Device mid-boiling point is condensed in -45 DEG C or more of ingredient, and boiling point does not condense in -45 DEG C of ingredients below into gas bomb；Reaction knot
It will be in condensed in two stages device in the liquids recovery to oil storage tank of condensation after beam.
Preferably, in step (1), high effectively hydrogen-carbon ratio raw material is that effective hydrogen-carbon ratio is discarded higher than the carbonaceous solids of setting value
Object (such as vinyon, polypropylene plastics or polystyrene plastics etc.), low effective hydrogen-carbon ratio raw material are that effective hydrogen-carbon ratio is low
In the carbonaceous solids waste (such as biomass etc.) of setting value；Height effectively hydrogen-carbon ratio raw material and low effective hydrogen-carbon ratio raw material are matched
Than that should so that the effective hydrogen-carbon ratio of mixed raw material is 0.8~1.4.
Preferably, in the step (1), catalyst LOSA-1, FCC or Al2O3One or more of it is mixed
It closes.
Preferably, in the step (1), the height effectively hydrogen-carbon ratio raw material particle size of selection is sieved to 80-120 mesh, selection
Low effective hydrogen-carbon ratio raw material particle size is between 70-100 mesh, and catalyst particle size is between 150-230 mesh.
Preferably, in the step (2), the temperature of the catalytic pyrolysis reaction occurred in fluidized bed pyrolyzer should control
Within the scope of 450-650 DEG C.
Preferably, the liquid fuel rich in aromatic hydrocarbon that catalysis pyrolysis generates, level-one condensation dress are received in the oil storage tank
Based on bicyclic indenes and naphthalene race product, the condensed product in B grade condensing unit is the product set with monocycle benzene type organic
It is main；It is pyrolyzed obtained incondensable gas and is rich in alkene.
Advantageous effect：High and low effective hydrogen-carbon ratio raw material provided by the invention be blended catalysis pyrolysis produce fuel device and
Method, compared with prior art, the invention has the advantages that：
1, the biomass class carbon raw material that the present invention can make effective hydrogen-carbon ratio low is converted into liquid combustion efficiently at low cost
Material, target product high conversion rate, the coke that pyrolytic process generates is few, and catalyst inactivation situation is compared to biography in catalysis pyrolytic process
System catalysis pyrolytic process mitigates significantly, and the service life of catalyst is made to extend, and dosage is reduced；
2, in the present invention, the product surcharge that catalysis pyrolysis is blended in different effectively hydrogen-carbon ratio raw materials is high, liquid product life
Object oil aromatic hydrocarbon content is high, mononuclear aromatic high selectivity, it is not necessary to the catalytic hydrogenation process for upgrading Jing Guo complex and expensive
It is directly used as fuel or chemicals raw material；Gas-phase product olefine selective is good, can also be used as industrial chemicals use；
3, the present invention is used as high effectively hydrogen-carbon ratio raw material using waste plastics such as vinyons, compared to tradition such as hydrogen
" hydrogen source " is at low cost, not only can greatly improve effective hydrogen-carbon ratio of charging, while between waste plastics and biomass preferably
Synergistic effect, also can preferably promote the reactions such as the depolymerization of both sides, fragrant isomerization；Therefore grind device provided by the invention and
Method is not only expected to solve the environmental problem of puzzlement social development, but also the efficient catalytic of both sides can also be promoted to convert, and realizes useless
Abandon the efficient utilization of resource.
Description of the drawings
The structural schematic diagram of Fig. 1 apparatus of the present invention.
Specific implementation mode
The present invention will be described with reference to the accompanying drawings.
Embodiment 1
The device that fuel is produced in catalysis pyrolysis, packet is blended for high and low effective hydrogen-carbon ratio raw material that this example uses as shown in Figure 1
Include premixed device 1, level-one motor 2, two level motor 3, feed bin 4, level-one feeding screw 5, deuterostrophies feeder 6, fluid bed heat
Solve device 7, cyclone separator 8, coke bin 9, level-one condensing unit 10, B grade condensing unit 11, oil storage tank 12 and air accumulator 13.
For the height effectively hydrogen-carbon ratio raw material that this example uses for vinyon, low effective hydrogen-carbon ratio raw material is pine sawdust, mixing
Mass ratio is 4:1；Catalyst choice partly inactivates FCC；Charging rate 21g/h；Catalyst 30mL；The screening of vinyon grain size is arrived
80-120 mesh, for pine sawdust grain size between 70-100 mesh, half inactivates FCC grain sizes between 150-230 mesh.
Pine sawdust, vinyon are mixed in premixed device 1, into feed bin 4, feed bin gas auxiliary is opened and feeds and prevent
Back-mixing.Feed bin gas is nitrogen, flow 100mL/min.Level-one feeding screw 5, deuterostrophies feeder 6 are opened, in feed bin 4
Screw rod of the mixed raw material through level-one feeding screw 5, deuterostrophies feeder 6 be forced into fluidized bed pyrolyzer 7.
7 internal diameter 32mm of fluidized bed pyrolyzer, air distribution plate are made of 316 stainless steel cloths of 300 mesh, and fluidized gas is nitrogen,
Tolerance is 250mL/min, and bed material is half inactivation FCC.Bed temperature is 600 DEG C in the fluid bed, and catalytic pyrolysis reaction occurs, and is occurred
Hydrogen migration, product enter cyclone separator 8；Gas-solid phase separation is carried out in cyclone separator 8, is inactivated after solid product reaction
The charcoal particle that catalyst and reaction generate, into coke bin 9, gas-phase product is the volatile matter that pyrolysis generates, and is condensed into level-one
Device 10.
Biomass pyrolytic gas phase product passes through level-one condensing unit 10, and boiling point stays in test tube in 0 DEG C or more of ingredient condensation
In, boiling point enters B grade condensing unit 11 0 DEG C of ingredient below is uncooled, 11 mid-boiling point of B grade condensing unit -45 DEG C with
On ingredient condensation, boiling point do not condense in -45 DEG C of ingredients below into gas bomb 13.
Experiment closes the 5 stopping charging of level-one feeding screw after starting 20min.Deuterostrophies feeder 6 is closed after 40min
Stop feed bin wind.Experiment terminates the liquid in condensed in two stages device injecting oil storage tank 12.
In gained pyrolysis product, fragrant Auditory steady-state responses are 36%, and pure pine sawdust catalysis pyrolysis aromatic hydrocarbon yield is only
7.1%.C2-C4Olefins yield is 35%, and pure pine sawdust catalysis pyrolysis C2-C4Olefins yield only has 6.6%.Using this case
Device and method can get up to 71% total chemicals yield altogether.And the catalysis of pure pine sawdust is pyrolyzed total chemicals yield only
Have 13.7%, total chemicals yield of pure vinyon catalysis pyrolysis also only has 59.8%.Pine sawdust is total with vinyon
Total chemicals yield that mixed catalysis pyrolysis obtains is significantly larger than pine sawdust and is individually catalyzed the result of pyrolysis with vinyon, it was demonstrated that
Two kinds of raw materials are acted synergistically in total catalysis pyrolytic process.Meanwhile the coke yield that catalysis pyrolysis is blended is 6.5%,
Far fewer than pine sawdust individually be catalyzed pyrolysis 38% charcoal yield, it was demonstrated that the device and method of this example play really reduce coking,
Enhance the effect of product conversion.
Embodiment 2
As shown in Figure 1, implementation and embodiment 1 are identical.
High effectively hydrogen-carbon ratio raw material is vinyon, and low effective hydrogen-carbon ratio raw material is cellulose, and mixing quality ratio is 2:
1；Catalyst choice partly inactivates FCC；Charging rate 21g/h；Catalyst 30mL；Vinyon grain size is sieved to 80-120 mesh,
For cellulose grain size between 70-100 mesh, half inactivates FCC grain sizes between 150-230 mesh.
Cellulose, vinyon are mixed in premixed device 1, into feed bin 4, feed bin gas auxiliary is opened and feeds and prevent
Back-mixing.Feed bin gas is nitrogen, flow 100mL/min.Level-one feeding screw 5, deuterostrophies feeder 6 are opened, in feed bin 4
Screw rod of the mixed raw material through level-one feeding screw 5, deuterostrophies feeder 6 be forced into fluidized bed pyrolyzer 7.
7 internal diameter 32mm of fluidized bed pyrolyzer, air distribution plate are made of 316 stainless steel cloths of 300 mesh, and fluidized gas is nitrogen,
Tolerance is 250mL/min, and bed material is half inactivation FCC.Bed temperature is 600 DEG C in the fluid bed, and catalytic pyrolysis reaction occurs, and is occurred
Hydrogen migration, product enter cyclone separator 8；Gas-solid phase separation is carried out in cyclone separator 8, is inactivated after solid product reaction
The charcoal particle that catalyst and reaction generate, into coke bin 9, gas-phase product is the volatile matter that pyrolysis generates, and is condensed into level-one
Device 10.
Biomass pyrolytic gas phase product passes through level-one condensing unit 10, and boiling point stays in test tube in 0 DEG C or more of ingredient condensation
In, boiling point enters B grade condensing unit 11 0 DEG C of ingredient below is uncooled, 11 mid-boiling point of B grade condensing unit -45 DEG C with
On ingredient condensation, boiling point do not condense in -45 DEG C of ingredients below into gas bomb 13.
Experiment closes the 5 stopping charging of level-one feeding screw after starting 20min.Deuterostrophies feeder 6 is closed after 40min
Stop feed bin wind.Experiment terminates the liquid in condensed in two stages device injecting oil storage tank 12.
In gained pyrolysis product, fragrant Auditory steady-state responses are 33.4%, and pure cellulose catalysis pyrolysis aromatic hydrocarbon yield is only
12.67%.C2-C4Olefins yield is 21.69%, and pure cellulose catalysis pyrolysis C2-C4Olefins yield only has 7.86%.Using
The device and method of this example can get up to 55.09% total chemicals yield altogether.And the total chemistry of catalysis pyrolysis of pure cellulose
Product yield only has 20.53%.Total chemicals yield that catalysis pyrolysis obtains is blended with vinyon and is significantly larger than fibre for cellulose
Dimension element is individually catalyzed being pyrolyzed as a result, and significantly larger than cellulose is catalyzed the weighted value of pyrolysis, card with vinyon respectively
Bright two kinds of raw materials in total catalysis pyrolytic process are acted synergistically.Meanwhile the coke yield that catalysis pyrolysis is blended is
15.45%, the charcoal yield of pyrolysis 34.81% is individually catalyzed far fewer than cellulose, it was demonstrated that the device and method of this example play really
Reduce the effect of coking, enhancing product conversion.
Embodiment 3
As shown in Figure 1, implementation and embodiment 1 are identical.
High effectively hydrogen-carbon ratio raw material is vinyon, and low effective hydrogen-carbon ratio raw material is lignin, and mixing quality ratio is 2:
1；Catalyst choice partly inactivates FCC；Charging rate 21g/h；Catalyst 30mL；Vinyon grain size is sieved to 80-120 mesh,
For cellulose grain size between 70-100 mesh, half inactivates FCC grain sizes between 150-230 mesh.
Lignin, vinyon are mixed in premixed device 1, into feed bin 4, feed bin gas auxiliary is opened and feeds and prevent
Back-mixing.Feed bin gas is nitrogen, flow 100mL/min.Level-one feeding screw 5, deuterostrophies feeder 6 are opened, in feed bin 4
Screw rod of the mixed raw material through level-one feeding screw 5, deuterostrophies feeder 6 be forced into fluidized bed pyrolyzer 7；
7 internal diameter 32mm of fluidized bed pyrolyzer, air distribution plate are made of 316 stainless steel cloths of 300 mesh, and fluidized gas is nitrogen,
Tolerance is 250mL/min, and bed material is half inactivation FCC.Bed temperature is 600 DEG C in the fluid bed, and catalytic pyrolysis reaction occurs, and is occurred
Hydrogen migration, product enter cyclone separator 8；Gas-solid phase separation is carried out in cyclone separator 8, is inactivated after solid product reaction
The charcoal particle that catalyst and reaction generate, into coke bin 9, gas-phase product is the volatile matter that pyrolysis generates, and is condensed into level-one
Device 10.
Biomass pyrolytic gas phase product passes through level-one condensing unit 10, and boiling point stays in test tube in 0 DEG C or more of ingredient condensation
In, boiling point enters B grade condensing unit 11 0 DEG C of ingredient below is uncooled, 11 mid-boiling point of B grade condensing unit -45 DEG C with
On ingredient condensation, boiling point do not condense in -45 DEG C of ingredients below into gas bomb 13.
Experiment closes the 5 stopping charging of level-one feeding screw after starting 20min.Deuterostrophies feeder 6 is closed after 40min
Stop feed bin wind.Experiment terminates the liquid in condensed in two stages device injecting oil storage tank 12.
In gained pyrolysis product, fragrant Auditory steady-state responses are 25.94%, and Vinsol's catalysis pyrolysis aromatic hydrocarbon yield is only
4.62%.C2-C4Olefins yield is 20.1%, and Vinsol catalysis pyrolysis C2-C4Olefins yield only has 3.19%.Using this
The device and method of example can get up to 46.03% total chemicals yield altogether.And the catalysis of pure pine sawdust is pyrolyzed total chemicals
Yield only has 7.81%.Total chemicals yield that catalysis pyrolysis obtains is blended with vinyon and is significantly larger than lignin for lignin
Individually catalysis pyrolysis as a result, and be catalyzed the weighted value of pyrolysis respectively slightly larger than lignin and vinyon, it was demonstrated that altogether
Two kinds of raw materials are acted synergistically in catalysis pyrolytic process.Meanwhile the coke yield that catalysis pyrolysis is blended is 16.09%, far
Less than lignin individually be catalyzed pyrolysis 44.06% charcoal yield, it was demonstrated that the device and method of this example play really reduce coking,
Enhance the effect of product conversion.
In conjunction with above-described embodiment as can be seen that the present invention solves effective hydrogen-carbon ratio raw material conversion difficulty low at present, pyrolysis
Product qualities are high, poor selectivity, the fast problem of the easy coking of catalyst, inactivation.Made simultaneously using waste plastics such as vinyons
It is at low cost compared to the tradition such as hydrogen " hydrogen source " for high effectively hydrogen-carbon ratio raw material, it is not only expected to solve the ring of puzzlement social development
Border problem, and the efficient catalytic of both sides can also be promoted to convert, realize the efficient utilization of waste resource.
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. the device that fuel is produced in catalysis pyrolysis is blended in a kind of high and low effective hydrogen-carbon ratio raw material, it is characterised in that：Including premixed device
(1), level-one motor (2), two level motor (3), feed bin (4), level-one feeding screw (5), deuterostrophies feeder (6), fluidisation
Bed pyrolysis apparatus (7), cyclone separator (8), coke bin (9), level-one condensing unit (10), B grade condensing unit (11), oil storage tank
(12) and air accumulator (13)；
The outlet of the premixed device (1) is connected with the entrance of feed bin (4), and the outlet of feed bin (4) is located at level-one feeding screw (5)
Inlet, level-one feeding screw (5) and level-one motor (2) are coaxially connected, by level-one motor (2) drive level-one spiral into
Glassware (5), the entrance of deuterostrophies feeder (6) are located at the exit of level-one feeding screw (5), deuterostrophies feeder
(6) outlet is connected with the entrance of fluidized bed pyrolyzer (7), and deuterostrophies feeder (6) and two level motor (3) are coaxially connected,
Deuterostrophies feeder (6) is driven by two level motor (3)；Deuterostrophies feeder (6) duration of runs is level-one spiral
Twice of feeder (5), to ensure raw material that level-one feeding screw (5) is conveyed completely into the fluidized bed pyrolyzer
(7)；
The entrance of the upper gas outlet connection cyclone separator (8) of the fluidized bed pyrolyzer (7), cyclone separator (8)
Gaseous phase outlet is connected with the entrance of level-one condensing unit (10), the entrance of the solid-phase outlet and coke bin (9) of cyclone separator (8)
It is connected；
The gas vent of the level-one condensing unit (10) is connected with the entrance of B grade condensing unit (11), B grade condensing unit
(11) gas vent is connected with air accumulator (13) entrance, the bottom carrier gas of air accumulator (13) outlet and fluidized bed pyrolyzer (7)
Entrance is connected；After reaction in level-one condensing unit (10), B grade condensing unit (11) liquids recovery of condensation to oil storage
In tank (12)；
The level-one feeding screw (5) and deuterostrophies feeder (6) constitute two-stage screw feeding mechanism, and feed bin (4) passes through
Two-stage screw feeding mechanism and fluidized bed pyrolyzer (7) indirect communication prevent the carrier gas in fluidized bed pyrolyzer (7) from playing a reversed role pan feeding
Storehouse (4)；In order to ensure feed bin (4) not back-mixing, nitrogen is passed through in feed bin (4) as feed bin gas, the flow of feed bin gas is fluidisation
The 30%~50% of fluidisation throughput in bed pyrolysis apparatus (7).
2. the device that fuel is produced in catalysis pyrolysis, feature is blended in high and low effective hydrogen-carbon ratio raw material according to claim 1
It is：The level-one condensing unit (10) is made of test tube and cylinder body, in vitro injects deionized water, passes through latex between test tube
Pipe is connected to, and mixture of ice and water is held in cylinder body, test tube is immersed in the mixture of ice and water in cylinder body, makes deionized water in test tube
Temperature be maintained within the scope of 0~2 DEG C；The B grade condensing unit (11) is made of test tube and cylinder body, in vitro injects ice
Ethyl alcohol is connected between test tube by emulsion tube, dry ice is held in cylinder body, test tube is immersed in the dry ice in cylinder body so that test tube
The temperature of interior ice ethyl alcohol is maintained within the scope of -40~-45 DEG C.
3. the device that fuel is produced in catalysis pyrolysis, feature is blended in high and low effective hydrogen-carbon ratio raw material according to claim 1
It is：The air distribution plate of the fluidized bed pyrolyzer (7) is made of stainless steel cloth, and mesh diameter is 300 mesh；Fluidized bed pyrolyzer
(7) carrier gas in is nitrogen or the non-condensation gas that pyrolysis generates, and bed material is selected catalyst.
4. the method based on any described device of claims 1 to 3, it is characterised in that：Include the following steps：
(1) high and low effective hydrogen-carbon ratio raw material is blended：By high effectively hydrogen-carbon ratio raw material, low effective hydrogen-carbon ratio raw material in premixed device (1)
In be mixed and fed into feed bin (4), opening feed bin gas auxiliary and feeding simultaneously prevents back-mixing, and the mixed raw material in feed bin (4) is through level-one spiral shell
The screw rod of precession glassware (5) and deuterostrophies feeder (6) is forced into fluidized bed pyrolyzer (7)；The high available hydrogen carbon
It is the carbonaceous solids waste that effective hydrogen-carbon ratio is higher than setting value than raw material, low effective hydrogen-carbon ratio raw material is that effective hydrogen-carbon ratio is less than
The carbonaceous solids waste of setting value；The high effectively proportioning of hydrogen-carbon ratio raw material and low effective hydrogen-carbon ratio raw material should make mixed
The effective hydrogen-carbon ratio of raw material is 0.8~1.4；
(2) catalysis pyrolysis is blended in high and low effective hydrogen-carbon ratio raw material：High and low effective hydrogen-carbon ratio raw material is with catalyst in fluid bed heat
It solves and catalytic pyrolysis reaction occurs in device (7), hydrogen migration occurs, product enters cyclone separator (8), in cyclone separator (8)
Carrying out gas-solid phase separation, solid product is the charcoal particle that the catalyst that inactivates and reaction generate after reaction, into coke bin (9),
Gas-phase product is the volatile matter that pyrolysis generates, into level-one condensing unit (10)；The catalyst is LOSA-1, FCC or Al2O3
One or more of mixing；
(3) high-quality liquid fuel is produced in condensation：Biomass pyrolytic gas phase product passes through level-one condensing unit (10), and boiling point is 0
DEG C or more ingredient condensation stay in test tube, boiling point enters B grade condensing unit (11), two level 0 DEG C of ingredient below is uncooled
Condensing unit (11) mid-boiling point is condensed in -45 DEG C or more of ingredient, and boiling point does not condense in -45 DEG C of ingredients below into gas bomb
(13)；It after reaction will be in the liquids recovery of condensation in condensed in two stages device to oil storage tank (12).
5. according to the method described in claim 4, it is characterized in that：In the step (1), the height effectively hydrogen-carbon ratio raw material of selection
Grain size is sieved to 80-120 mesh, and low effective hydrogen-carbon ratio raw material particle size of selection is between 70-100 mesh, and catalyst particle size is between 150-
230 mesh.
6. according to the method described in claim 4, it is characterized in that：In the step (2), occur in fluidized bed pyrolyzer (7)
The temperature of catalytic pyrolysis reaction should control within the scope of 450-650 DEG C.
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| CN112760116B (en) * | 2020-11-24 | 2022-09-09 | 中国科学院广州能源研究所 | Pyrolysis-separation integrated device and process for directionally preparing high-valued products from plastic wastes |
| CN113462410B (en) * | 2021-07-30 | 2022-09-30 | 重庆大学 | Infrared rapid heating medical waste's pyrolysis polygeneration system |
| CN114874800A (en) * | 2022-05-10 | 2022-08-09 | 东南大学 | Biomass-based organic liquid hydrogen storage system and method |
| CN116254127A (en) * | 2023-01-12 | 2023-06-13 | 中国石油大学(北京) | Device and method for preparing fuel by catalytic pyrolysis of waste plastics |
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