CN107022368A - A kind of adhesive sticker pyrolysis of waste trans-utilization system and method - Google Patents
A kind of adhesive sticker pyrolysis of waste trans-utilization system and method Download PDFInfo
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- CN107022368A CN107022368A CN201610069210.5A CN201610069210A CN107022368A CN 107022368 A CN107022368 A CN 107022368A CN 201610069210 A CN201610069210 A CN 201610069210A CN 107022368 A CN107022368 A CN 107022368A
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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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- 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
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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
- C10G2300/1003—Waste materials
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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
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Gasification And Melting Of Waste (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention relates to a kind of adhesive sticker pyrolysis of waste trans-utilization system and method, the system is made up of catalysis pyrolysis unit, burning with catalyst regeneration units.Methods described is：Adhesive sticker discarded object fires the quick heating of grey thermal cyclic carrier by high temperature, and occurs catalysis fast pyrogenation in the presence of calcium oxide in high temperature combustion ash, obtains higher efficiency of carbon con version, and produce pyrolysis oil, gas product；Decomposition of Calcium Carbonate in combustion ash can be generated calcium oxide by the heat that pyrolysis char is produced through high-temp combustion, so as to realize the regeneration of calcium based catalysts, it is not necessary to supplement and extra catalyst.The present invention efficiently solves processing and the handling problems of adhesive sticker discarded object, and pyrolysis oil, the gas product of high-quality are prepared by thermal transition technology, and co-production richness calcium material realizes harmless treatment and the recycling of adhesive sticker discarded object.
Description
Technical field
The present invention relates to solid waste processing and recycle and derived energy chemical field, a kind of do not done specifically, being related to
Glue pyrolysis of waste trans-utilization system and method.
Background technology
Adhesive sticker (English name：Pressure-sensitive adhesive, PSA), also known as self-adhesive label material,
It is that, using paper, plastics, film or special material as fabric, the back side scribbles adhesive, is answered using the one kind for applying silicon protection sheet as base stock
Condensation material, is widely used in the fields such as product packaging, material mark.Since 2011, China's adhesive label market demand
The continuous expansion of amount, to be often close on 20% ratio rapid growth.Meanwhile, produced in adhesive label production and consumption process
Discarded object amount also increases year by year.According to statistics, the only annual waste material produced in new label printing production link in Shanghai City is up to 30000
Ton.Compared to traditional solid waste rubbish, adhesive sticker discarded object has its particularity again.Due to the presence of high viscosity pressure sensitive adhesive, lead
Cause adhesive sticker to be bonded together with the conventional solid waste such as a large amount of wrapping papers, plastics, cloth to be difficult to separate, increase adhesive sticker discarded object
Discharge capacity, also increases the difficulty of offal treatment.In addition, adhesive sticker discarded object often contains chlorine, fluorine element, especially work as raw material
Constitute as PVC, neoprene, during the material such as fluoroplastics, chlorine, fluorine element content are higher.These are chloride, the presence of fluorine material, lead
Adhesive sticker discarded object is caused to be handled as bulk solid waste frequently with the treating method burned and filled.Therefore, no
Dry glue discarded object has been prohibited to handle with buried method to burn.At present, the processing for such discarded object is reclaimed except a small amount of
Using outer, substantially using processing is stored up, this not only occupies a large amount of soils, also add environmental pressure, cause the wasting of resources,
The problems such as environmental pollution.Obviously, reality of the processing of adhesive sticker discarded object with disposal as restriction adhesive sticker industry development is asked
Topic.On the other hand, adhesive sticker discarded object is derived from chemical products, and its composition is predominantly rich in hydrocarbon organic material, and traditional burns
Burning and landfill can cause the waste of valuable resource, if by adhesive sticker discarded object by thermochemical study be high value added product,
The problem of adhesive sticker discarded object end-o f-pipe -control can be solved.In addition, the adhesive label of China 80% is stationery adhesive sticker according to statistics
Label material.Carbon in conventional label paper, package paper (such as white board, brown paper), printing (such as art paper) paper wood
The addition of sour calcium filler is up to 10~40%, during thermochemical study, pyrolysis, gasification of the inorganic calcium salt for organic matter
Reaction has notable catalytic action, therefore, there is beneficial to the carbon conversion for improving thermal conversion reaction the presence of calcium salt in waste materials
Rate, but also pyrolysis oil, gas quality can be improved.Therefore, the above-mentioned special nature of adhesive sticker waste materials is made full use of, can be real
The recycling of existing discarded object, produces good environmental benefit and economic benefit, further promotes China's adhesive sticker industry
Development.
Based on background above, the application is directed to the property of adhesive sticker waste materials, proposes a kind of adhesive sticker castoff heat
Trans-utilization system and method is solved, to solve the problem of adhesive sticker offal treatment and disposal process are present, realizes that adhesive sticker gives up
The harmless treatment of gurry and recycling.
The content of the invention
It is an object of the present invention to provide a kind of adhesive sticker pyrolysis of waste trans-utilization system and method, the system and
Method can realize the harmless treatment of adhesive sticker discarded object.
, should it is a further object of the invention to provide a kind of adhesive sticker pyrolysis of waste trans-utilization system and method
System and method prepares adhesive sticker discarded object by thermal transition oil, gas alternative fuel or the industrial chemicals of high added value, in parallel
The rich calcium material of production, realizes the recycling of adhesive sticker discarded object.
A kind of adhesive sticker pyrolysis of waste trans-utilization system and method proposed by the present invention, it is former using adhesive sticker discarded object
Contain the special nature of a large amount of ingredients calcium carbonates in material, set up the recycle chemistry chain of calcium based catalysts, main technological route such as Fig. 1
It is shown.Adhesive sticker waste materials fire grey thermal cyclic carrier heating through high temperature and occurred in combustion ash under the catalytic action of calcium oxide
Quick catalysis pyrolytic reaction, obtains the pyrolysis oil and pyrolysis gas product of high-quality, and efficiency of carbon con version is higher.And fire active oxidation in ash
Calcium can absorb CO2Form calcium carbonate and cause its activity reduction or inactivate.Therefore, the heat that pyrolysis char is produced through high-temp combustion
Decomposition of Calcium Carbonate in combustion ash can be generated calcium oxide, so as to realize the regeneration of calcium based catalysts, and obtain rich calcium material.
To achieve these goals, the invention provides following technical scheme：
The adhesive sticker pyrolysis of waste trans-utilization system of the present invention, including adhesive sticker discarded object catalysis pyrolysis unit, combustion
Burn and catalyst regeneration units, wherein,
The adhesive sticker discarded object catalysis pyrolysis unit includes：Preprocessor 1, for being taken off to adhesive sticker discarded object
Chlorine, dewater treatment, while aging viscose, carries out the glutinous processing of drop, and,
Pyrolysis reactor 3, for the quick catalysis pyrolysis of adhesive sticker waste materials after pretreatment, produces pyrolysis oil, gas
Product and pyrolysis char, wherein,
The solid outlet of the bottom of preprocessor 1 is connected with the feeding-in solid body mouthful on the top of pyrolysis reactor 3, is pre-processed
The bottom of device 1 sets heating medium entrance；The bottom of pyrolysis reactor 3 sets pyrolysis char discharging opening.
The burning includes with catalyst regeneration units：
Combustion reactor 7, for the burning of pyrolysis char, produces high-temperature flue gas and high temperature combustion ash, and the carbon that will be fired in ash
Sour calcium is decomposed into calcium oxide, realizes the regeneration of calcium based catalysts, and,
Second gas-solid separating device 9, the separation of the flue gas and its entrained solid particles that are produced for combustion reactor 7, its
In,
The top exhanst gas outlet of combustion reactor 7 is connected with the entrance of the upper portion side wall of the second gas-solid separating device 9, burning
The thermal cyclic carrier discharging opening of the upper portion side wall of reactor 7 is connected with the upper feed inlet of pyrolysis reactor 3, the bottom of combustion reactor 7
The mixed material entrance of side wall is connected with the pyrolysis char discharging opening of pyrolysis reactor 3, and the bottom of combustion reactor 7 sets combustion-supporting gas
Air inlet and deslagging discharging opening；The bottom solid outlet of second gas-solid separating device 9 and the upper feed inlet of pyrolysis reactor 3
Connection.
The system according to the present invention, wherein, the adhesive sticker discarded object catalysis pyrolysis unit can also include the first gas-solid
Separator 4, the separation for being pyrolyzed gas mixture and its entrained solid particles, and gas-liquid separation device 5, for through gas-solid
Pyrolysis oil, the separation of gas product after separating treatment；
The charging aperture of first gas-solid separating device 4 is connected with the upper part discharge port of pyrolysis reactor 3, first gas
The gaseous product discharging opening of solid separation device 4 is connected with the charging aperture of gas-liquid separation device 5；The bottom of first gas-solid separating device 4
Solid product discharging opening is set；The bottom of gas-liquid separation device 5 sets product liquid discharging opening, the top of gas-liquid separation device 5 or on
Portion side wall sets gaseous product discharging opening；The solid product discharging opening of the bottom of first gas-solid separating device 4 and combustion reactor 7
The mixed material entrance connection of lower sides.
The system according to the present invention, wherein, the adhesive sticker discarded object catalysis pyrolysis unit can also include milk of lime and inhale
Receives pond 2, for absorbing the chlorine contained exhaust gas produced by preprocessor 1, the milk of lime absorption cell 2 and the top of preprocessor 1 or on
The chlorine contained exhaust gas outlet connection of portion side wall.
The system according to the present invention, wherein preferably, preprocessor 1 of the present invention can use reacting in rotary kiln
It is any in device, spiral drop flow reactor or blade stirring formula reactor with deflection plate；The preprocessor 1 is used and disturbed
Flow reverse mode of heating, realize heating medium with adhesive sticker discarded object material more uniformly, be sufficiently mixed.
The system according to the present invention, wherein preferably, the pyrolysis reactor 3 can use helical reactors or dial
Chip reactor；The combustion reactor 7 can be using circulating fluid bed reactor, fluidized bed furnace reactor or lifting pipe reaction
It is any in device.
The system according to the present invention, wherein, thermal cyclic carrier discharging opening and the pyrolysis of the upper portion side wall of combustion reactor 7
The connection of the upper feed inlet of reactor 3, or the thermal cyclic carrier discharging opening of the upper portion side wall of combustion reactor 7 and the first gas-solid point
From the connection of the bottom of device 4, connected mode well known in the art can be used, for example, conveyer belt, conveying worm or pipeline
Etc..Preferably, a material-returning device 6, its upper feed inlet and the pyrolysis char discharging opening of the bottom of pyrolysis reactor 3 can be set
Be connected, when being provided with the first gas-solid separating device 4, the upper feed inlet of the material-returning device 6 simultaneously with pyrolysis reactor 3
The pyrolysis char discharging opening of bottom and the solid product discharging opening of the bottom of the first gas-solid separating device 4 are connected；The returning charge dress
The discharging opening for putting 6 bottoms or sidepiece is connected with the mixed material entrance of the lower sides of combustion reactor 7.Described material-returning device 6
Can be non-mechanical means, such as returning charge U valves, L valves or mechanical device, such as guiding valve, conveying worm or piece-picking type are conveyed
Machine.
The system according to the present invention, wherein, the upper feed inlet of pyrolysis reactor 3 and the lower sides of combustion reactor 7
Mixed material entrance connection, or the upper feed inlet of pyrolysis reactor 3 and the bottom solids exit of the second gas-solid separating device 9
The connection of mouth, can use connected mode well known in the art, for example, conveyer belt, conveying worm or pipeline etc..It is preferred that
Ground, can set a heat carrier conveying device 8, the thermal cyclic carrier charging aperture on its top respectively with the upper side of combustion reactor 7
The thermal cyclic carrier discharging opening and the bottom solid outlet of the second gas-solid separating device 9 of wall are connected；The heat carrier conveying dress
The thermal cyclic carrier discharging opening for putting 8 bottoms is connected with the upper feed inlet of pyrolysis reactor 3.The carrier conveying device 8 can be
Non-mechanical means, such as returning charge U valves, L valves or mechanical device, such as guiding valve, conveying worm or piece-picking type conveyer.
Present invention also offers a kind of adhesive sticker pyrolysis of waste trans-utilization method based on said system, including it is following
Step：
1) will it is broken after adhesive sticker waste materials particle feeding preprocessor 1, it is inverse with the gas-phase heating medium that is passed through
Stream contact, raw material is sufficiently heated；
2) pretreated material enters pyrolysis reactor 3, is sufficiently mixed with the grey heat carrier of high temperature combustion of input, and in combustion
Quick catalysis pyrolysis is carried out in ash in the presence of calcium oxide, pyrolysis char and pyrolysis oil gas mix products is produced；
3) pyrolysis char for producing pyrolysis reactor 3 is delivered to combustion reactor 7, with being passed through by combustion reactor bottom
Combustion-supporting gas burn；Burnt in combustion reactor generation flue gas entrained solids fine ash particle enter the second gas solid separation
Device 9, the solid fine ash particle produced after separation returns to pyrolysis reactor 3；The high temperature combustion ash produced in combustion reactor 7 is defeated
Pyrolysis reactor 3 is delivered to, thermal source and calcium based catalysts are provided for pyrolytic process as active thermal cyclic carrier.
The method according to the invention, wherein, when the preprocessor 1 connects milk of lime absorption cell 2, the step 1) in
Raw material is sufficiently heated, and chlorine-bearing compound in raw material is decomposed generation hydrogen chloride, part organic matter occurs pyrolysis and produces a small amount of be pyrolyzed
Gas and water vapour, form chlorine contained exhaust gas, and enter milk of lime absorption cell 2 under heating medium flow field entrainment effect.Preferably, it is described
Milk of lime absorbing liquid used in milk of lime absorption cell 2 is saturation lime slurry, is made by rich calcium combustion ash with water mixture, configuration proportion
Determined according to calcium oxide content in combustion ash.Steam condensate (SC) that water can be produced preferably by preprocessor 1 is provided.Milk of lime
Absorbing liquid preparation raw material comes from internal system, and chlorine contained exhaust gas processing cost is not produced.
The method according to the invention, wherein, separate dress when being provided with the first gas-solid separating device 4 with gas-liquid separation device 5
When putting, the upper part discharge port of the pyrolysis reactor 3 is connected with the charging aperture of the first gas-solid separating device 4, the first gas solid separation
The gaseous product discharging opening of device 4 is connected with the charging aperture of gas-liquid separation device 5；
The method according to the invention, wherein, step 1) the gas-phase heating medium can be not dry in reaction initial period
Glue waste materials are directly entered combustion reactor 7, the high-temperature flue gas obtained through burning；, can be with systems during stable reaction
The high-temperature flue gas directly produced in combustion reactor 7 is delivered to preprocessor 1.
Step 2) in, the pyrolysis oil gas mix products that the pyrolysis reactor 3 is produced are through the first gas-solid separating device 4 and gas
Liquid separating apparatus 5 is separated, and respectively obtains pyrolysis oil and pyrolysis gas product；
Sent through the isolated fine grained of the first gas-solid separating device 4 together with the pyrolysis char that pyrolysis reactor 3 is produced
Enter combustion reactor 7；It can also select to be delivered to combustion reactor 7 by material-returning device 6.
The method according to the invention, after stable reaction in system, step 3) handled through the second gas-solid separating device 9 after
Flue gas can be used as gas-phase heating medium into preprocessor 1.Specifically, produced after the processing of the second gas-solid separating device 9 rich
Containing CO2The flue gas of gas is simultaneously discharged after processing, and a portion is passed through preprocessor 1 as heating medium.
Step 3) in separated through the second gas-solid separating device 9 after the solid fine ash particle and combustion reactor 7 that produce
The high temperature combustion ash of interior generation can also be conveyed when being delivered to pyrolysis reactor 3 by heat carrier conveying device 8.
Method in accordance with the invention it is preferred that it is described it is broken after the grain size of adhesive sticker waste materials particle be
0.1~10cm.
The method according to the invention, wherein, step 2) the grey heat carrier of high temperature combustion can be not in reaction initial period
Dry glue waste materials are directly entered combustion reactor 7, and the high temperature obtained through burning fires ash；, can in systems during stable reaction
Pyrolysis reactor 3 is delivered to the high temperature combustion ash directly produced in combustion reactor 7, recycled.
The method according to the invention, wherein, the heating medium is the heat smoke that pyrolysis char burning is produced, or is hot cigarette
One or more in the steam that gas heat exchange is produced, or the steam produced for the heat exchange of pyrolysis gas-phase product condensation process.When
After stable reaction in system, it is possible to use step 3) through the second gas-solid separating device 9 handle after flue gas be used as gas-phase heating
Medium.
The method according to the invention, wherein, the combustion-supporting gas is any of air, or oxygen, or oxygen rich gas.It is excellent
Selection of land, combustion-supporting gas uses oxygen, and obtain higher degree is rich in CO2Flue gas, can make CO2Industrial gas, reduces CO2Discharge capacity
Meanwhile, form the byproduct output of certain added value.CO in flue gas2, a part is that adhesive sticker pyrolysis of waste semicoke is abundant
Burning is produced, and another part produces for Decomposition of Calcium Carbonate.
The method according to the invention, wherein, the preprocessor 1, pyrolysis reactor 3 are with combustion reactor 7 using difference
The mode of temperature control, wherein, the temperature in preprocessor 1 is that the temperature in 150~350 DEG C, pyrolysis reactor 3 is 300~750
DEG C, the temperature in combustion reactor 7 is 700~1000 DEG C.Preferably, the temperature in preprocessor is 200~300 DEG C, pyrolysis
Temperature in reactor is 350~650 DEG C, and the temperature in combustion reactor is 750~950 DEG C.
Advantage of the invention is that：
(1) present invention proposes a kind of system and method for adhesive sticker pyrolysis of waste trans-utilization, is that China's adhesive sticker gives up
The harmless treatment of gurry provides a kind of new approach with recycling.
(2) chlorine contained exhaust gas that adhesive sticker castoff heat solution preocess is produced in the present invention is absorbed using lime slurry,
It is that mixture is obtained in proportion with water by combustion ash, its reclaimed water comes from and milk of lime absorbing liquid used in technology comes from internal system
The steam condensate (SC) that preprocessor is produced, the solid product that combustion ash is obtained during combustion reaction.Therefore, this technology will not
Chlorine contained exhaust gas is produced, so that extra exhaust-gas treatment cost will not be produced；The combustion ash and water of technique itself product are make use of simultaneously
As absorbing liquid, cost of material is further saved.
(3) it by the combustion of adhesive sticker discarded object ash as thermal cyclic carrier (not needing additional bed) is quick to be in the present invention
Pyrolytic reaction heat supply, wherein the calcium oxide component being rich in combustion ash has catalytic action to pyrolytic process, so that adhesive sticker is discarded
Thing pyrolytic process has higher transformation efficiency；And the calcium carbonate of pyrolytic process formation is thermally decomposed again under high temperature action
To calcium oxide, the regeneration of catalyst is realized.
(5) fire and calcium oxide component is rich in ash, and adhesive sticker pyrolysis of waste mistake is used as using the combustion ash rich in calcium oxide
The catalyst of journey, can obtain higher transformation efficiency, while effectively improving pyrolysis oil, the quality of gas product.In a word, ash is fired
In be rich in calcium oxide component, on the one hand can be catalyzed the deep pyrolytic of heavy component in pyrolysis oil, in reduction pyrolysis oil oxygen content and
The content of acidic materials, so as to improve the stability of pyrolysis oil；On the one hand also it can absorb the CO produced in pyrolytic process2, significantly
Reduce CO in pyrolysis gas2Content, while having catalytic action to water gas shift reation again, further increases the yield of hydrogen.
(6) pyrolysis of adhesive sticker discarded object can not only obtain pyrolysis oil, the gas product of high added value in the present invention, may be used also
Obtain the rich calcium material of coproduction.In addition, the flue gas that adhesive sticker pyrolysis of waste coal-char combustion is produced can also be used as richness CO2Gas products
Output, as industrial chemicals, while reducing carbon emission, further promotes harmless treatment and the resource of adhesive sticker discarded object
Change and utilize.
Brief description of the drawings
Fig. 1 is a kind of main technological route figure of adhesive sticker pyrolysis of waste trans-utilization method of the present invention.
Fig. 2 is a kind of structural representation of adhesive sticker pyrolysis of waste trans-utilization system of the present invention.
Fig. 3 is a kind of structural representation (the limy breast suction of adhesive sticker pyrolysis of waste trans-utilization system of the present invention
Receives pond).
Fig. 4 (contains the first gas-solid for a kind of structural representation of adhesive sticker pyrolysis of waste trans-utilization system of the present invention
Separator and gas-liquid separation device).
Fig. 5 is a kind of structural representation (the limy breast suction of adhesive sticker pyrolysis of waste trans-utilization system of the present invention
Receives pond, the first gas-solid separating device and gas-liquid separation device).
Fig. 6 (contains material-returning device for a kind of structural representation of adhesive sticker pyrolysis of waste trans-utilization system of the present invention
With heat carrier conveying device).
Reference
1st, preprocessor 2, milk of lime absorption cell 3, pyrolysis reactor
4th, the first gas-solid separating device 5, gas-liquid separation device 6, material-returning device
7th, combustion reactor 8, heat carrier conveying device 9, the second gas-solid separating device
Embodiment
The invention will be further described below in conjunction with the accompanying drawings.
As shown in Fig. 2 the adhesive sticker pyrolysis of waste trans-utilization system of the present invention, including adhesive sticker discarded object catalytic thermal
Unit, burning and catalyst regeneration units are solved, wherein,
The adhesive sticker discarded object catalysis pyrolysis unit includes：Preprocessor 1 and pyrolysis reactor 3, wherein, the pre- place
The solid outlet of reason device 1 bottom is connected with the feeding-in solid body mouthful on the top of pyrolysis reactor 3, and the bottom of preprocessor 1 sets heating
Medium entrance；The bottom of pyrolysis reactor 3 sets pyrolysis char discharging opening；
The burning includes with catalyst regeneration units：The gas-solid separating device 9 of combustion reactor 7 and second, wherein, it is described
The top exhanst gas outlet of combustion reactor 7 is connected with the entrance of the upper portion side wall of the second gas-solid separating device 9, the top of combustion reactor 7
The thermal cyclic carrier discharging opening of side wall is connected with the upper feed inlet of pyrolysis reactor 3, the mixture of the lower sides of combustion reactor 7
Material entrance is connected with the pyrolysis char discharging opening of pyrolysis reactor 3, and the bottom of combustion reactor 7 sets and helps gas inlet and deslagging
Discharging opening；The bottom solid outlet of second gas-solid separating device 9 is connected with the upper feed inlet of pyrolysis reactor 3.
As shown in figure 4, it is further preferred that adhesive sticker discarded object catalysis pyrolysis unit can also include the first gas-solid
Separator 4 and gas-liquid separation device 5, the pyrolysis oil gas mix products to handle the generation of pyrolysis reactor 3.First gas
The charging aperture of solid separation device 4 is connected with the upper part discharge port of pyrolysis reactor 3, the gas of first gas-solid separating device 4
Product discharge mouthful is connected with the charging aperture of gas-liquid separation device 5；The bottom of first gas-solid separating device 4 sets solid product to discharge
Mouthful；The bottom of gas-liquid separation device 5 sets product liquid discharging opening, and the top of gas-liquid separation device 5 or upper portion side wall set gas to produce
Thing discharging opening；The mixture of the solid product discharging opening of the bottom of first gas-solid separating device 4 and the lower sides of combustion reactor 7
Expect entrance connection.
As shown in Figures 3 and 5, it is further preferred that adhesive sticker discarded object catalysis pyrolysis unit also includes milk of lime suction
The chlorine contained exhaust gas outlet of receives pond 2, the top of the milk of lime absorption cell 2 and preprocessor 1 or upper portion side wall is connected, for absorb by
The chlorine contained exhaust gas that preprocessor 1 is produced.
As shown in fig. 6, still further preferably, a material-returning device 6, its upper feed inlet and pyrolysis reactor can be set
The pyrolysis char discharging opening of 3 bottoms is connected, when being provided with the first gas-solid separating device 4, and the top of the material-returning device 6 is entered
Material mouth goes out with the pyrolysis char discharging opening of the bottom of pyrolysis reactor 3 and the solid product of the bottom of the first gas-solid separating device 4 simultaneously
Material mouth is connected；The discharging opening of the bottom of material-returning device 6 or sidepiece and the mixed material entrance of the lower sides of combustion reactor 7
Connection.
One heat carrier conveying device 8 can also be set, the thermal cyclic carrier charging aperture on its top respectively with combustion reactor 7
The thermal cyclic carrier discharging opening and the bottom solid outlet of the second gas-solid separating device 9 of upper portion side wall are connected；The heat carrier
The thermal cyclic carrier discharging opening of the bottom of conveying device 8 is connected with the upper feed inlet of pyrolysis reactor 3.
As shown in Fig. 2 when the adhesive sticker pyrolysis of waste trans-utilization system for using the present invention is not done for converting
During glue discarded object, comprise the following steps：
1) will it is broken after adhesive sticker waste materials particle feeding preprocessor 1, it is inverse with the gas-phase heating medium that is passed through
Stream contact, raw material is sufficiently heated；
2) pretreated material enters pyrolysis reactor 3, is sufficiently mixed with the grey heat carrier of high temperature combustion of input, and in combustion
Quick catalysis pyrolysis is carried out in ash in the presence of calcium oxide, pyrolysis char and pyrolysis oil gas mix products is produced；
3) pyrolysis char for producing pyrolysis reactor 3 is delivered to combustion reactor 7, with being passed through by combustion reactor bottom
Combustion-supporting gas burn；Burnt in combustion reactor generation flue gas entrained solids fine ash particle enter the second gas solid separation
Device 9, the solid fine ash particle produced after separation returns to pyrolysis reactor 3；The high temperature combustion ash produced in combustion reactor 7 is defeated
Pyrolysis reactor 3 is delivered to, thermal source and calcium based catalysts are provided for pyrolytic process as active thermal cyclic carrier.
As shown in figure 3, when the preprocessor 1 connects milk of lime absorption cell 2, the step 1) in raw material by fully plus
Heat, makes chlorine-bearing compound in raw material decompose generation hydrogen chloride, part organic matter occurs pyrolysis and produces a small amount of pyrolysis gas and water vapour,
Chlorine contained exhaust gas is formed under the entrainment effect of heating medium flow field, and enters milk of lime absorption cell 2.
As shown in figure 4, when being provided with the first gas-solid separating device 4 with 5 separator of gas-liquid separation device, the pyrolysis
The upper part discharge port of reactor 3 is connected with the charging aperture of the first gas-solid separating device 4, the gas production of the first gas-solid separating device 4
Thing discharging opening is connected with the charging aperture of gas-liquid separation device 5；The pyrolysis oil gas mix products that the pyrolysis reactor 3 is produced are through the
One gas-solid separating device 4 is separated with gas-liquid separation device 5, respectively obtains pyrolysis oil and pyrolysis gas product；Through the first gas solid separation
The isolated fine grained of device 4 sends into combustion reactor 7 together with the pyrolysis char that pyrolysis reactor 3 is produced.
Embodiment 1
The adhesive sticker waste materials for being broken to 1~5cm are sent into rotary kiln preprocessor, with rotary kiln preprocessor bottom
It is sufficiently heated after the heat smoke heating medium counter flow contact being passed through, rotary kiln preprocessor temperature control is at 240 DEG C.Adhesive sticker
Chlorine-bearing compound in discarded object is decomposed generation hydrogen chloride, and milk of lime absorption cell is entered under the entrainment of heating medium flow field；In advance
Material after processing enters piece-picking type pyrolysis reactor, and the high temperature combustion ash sent with heat carrier conveying device is sufficiently mixed, and
Quick catalysis pyrolysis is carried out in the presence of calcium oxide in combustion ash, piece-picking type pyrolysis reactor temperature control produces pyrolysis at 500 DEG C
Semicoke and pyrolysis oil gas mix products；Oil gas mix products are pyrolyzed to separate through the first gas-solid separating device, gas-liquid separation device, point
Pyrolysis oil and pyrolysis gas product are not obtained, through the isolated fine grained of the first gas-solid separating device and piece-picking type pyrolysis reactor
Pyrolysis char, the grey heat carrier mixed material of low temperature combustion of generation together enter material-returning device, then are delivered to circulation by material-returning device
Fluidized bed combustion reactor, the air-breathing gas generation combustion reaction with being passed through by CFBC reactor bottom, is followed
Circulation fluidized bed combustion reactor is controlled at 1000 DEG C；Burnt in CFBC reactor the flue gas entrained solids of generation
Fine ash particle enters the second gas-solid separating device, and the solid fine ash particle produced after separation enters heat carrier conveying device；Through
Flue gas discharge after processing, a portion is pre-processed as heating medium to material；CFBC reactor
The high temperature combustion ash of interior generation is quantitatively transferred to piece-picking type pyrolysis reactor through heat carrier conveying device, is used as active thermal cyclic carrier
Thermal source and calcium based catalysts are provided for pyrolytic process, remaining high temperature combustion ash is discharged through slag-drip opening.
Embodiment 2
The present embodiment, using experimental method and step same as Example 1, difference is adhesive sticker waste materials
Particle size is controlled in 0.1~1cm；Preprocessor uses the blade stirring formula preprocessor with deflection plate, preprocessor temperature
Degree control is at 350 DEG C；Heat the steam that medium uses heat smoke heat exchange to produce；Combustion-supporting gas uses oxygen rich gas；Pyrolytic reaction
Device uses spiral pyrolysis reactor, and pyrolysis reactor temperature control is at 650 DEG C；Combustion reactor is using lifting tubular type combustion reaction
Device, combustion reactor temperature control is at 700 DEG C.
Embodiment 3
The present embodiment, using experimental method and step same as Example 1, difference is adhesive sticker waste materials
Particle size is controlled in 5~10cm；Preprocessor drops streaming preprocessor using spiral, and preprocessor temperature control is at 150 DEG C；
Heat the steam that medium is produced using the heat exchange of pyrolysis gas-phase product condensation process；Combustion-supporting gas uses oxygen；Pyrolysis reactor is adopted
With spiral pyrolysis reactor, pyrolysis reactor temperature control is at 300 DEG C；Combustion reactor uses boiling furnace combustion reactor, combustion
Temperature of reactor control is burnt at 850 DEG C；
Non-elaborated part of the present invention belongs to techniques well known.
Certainly, the present invention can also have various embodiments, in the case of without departing substantially from spirit of the invention and its essence, be familiar with
Those skilled in the art can make various corresponding changes and deformation according to disclosure of the invention, but these it is corresponding change and
Deformation should all belong to the scope of the claims of the present invention.
Claims (14)
1. a kind of adhesive sticker pyrolysis of waste trans-utilization system, including adhesive sticker discarded object catalysis pyrolysis unit, burn and urge
Agent regeneration unit, it is characterised in that
The adhesive sticker discarded object catalysis pyrolysis unit includes：Preprocessor (1) and pyrolysis reactor (3), wherein,
The solid outlet of preprocessor (1) bottom is connected with the feeding-in solid body mouthful on pyrolysis reactor (3) top, is pre-processed
Device (1) bottom sets heating medium entrance；The bottom of pyrolysis reactor (3) sets pyrolysis char discharging opening；
The burning includes with catalyst regeneration units：
Combustion reactor (7) and the second gas-solid separating device (9), wherein,
Exhanst gas outlet is connected with the entrance of the second gas-solid separating device (9) upper portion side wall at the top of the combustion reactor (7), is burnt
The thermal cyclic carrier discharging opening of reactor (7) upper portion side wall is connected with pyrolysis reactor (3) upper feed inlet, combustion reactor
(7) the mixed material entrance of lower sides is connected with the pyrolysis char discharging opening of pyrolysis reactor (3), combustion reactor (7) bottom
Portion sets and helps gas inlet and deslagging discharging opening；Second gas-solid separating device (9) the bottom solid outlet is anti-with pyrolysis
Device (3) upper feed inlet is answered to connect.
2. system according to claim 1, it is characterised in that the adhesive sticker discarded object catalysis pyrolysis unit also includes the
One gas-solid separating device (4) and gas-liquid separation device (5), the charging aperture and pyrolytic reaction of first gas-solid separating device (4)
The upper part discharge port connection of device (3), the gaseous product discharging opening and gas-liquid separation device of first gas-solid separating device (4)
(5) charging aperture connection；First gas-solid separating device (4) bottom sets solid product discharging opening；Gas-liquid separation device (5) bottom
Set at the top of product liquid discharging opening, gas-liquid separation device (5) or upper portion side wall sets gaseous product discharging opening；First gas-solid point
Solid product discharging opening from device (4) bottom is connected with the mixed material entrance of the lower sides of combustion reactor (7).
3. system according to claim 1 or 2, it is characterised in that the adhesive sticker discarded object catalysis pyrolysis unit is also wrapped
Milk of lime absorption cell (2) is included, the milk of lime absorption cell (2) and the chlorine contained exhaust gas at preprocessor (1) top or upper portion side wall go out
Mouth connection.
4. system according to claim 1, it is characterised in that the burning also includes returning charge with catalyst regeneration units and filled
Put (6) and heat carrier conveying device (8), the upper feed inlet of the material-returning device (6) and the pyrolysis of pyrolysis reactor (3) bottom
Semicoke discharging opening is connected, the discharging opening of material-returning device (6) bottom or sidepiece and mixing for combustion reactor (7) lower sides
Close material inlet connection；
The thermal cyclic carrier charging aperture on the top of the heat carrier conveying device (8) respectively with combustion reactor (7) upper portion side wall
Thermal cyclic carrier discharging opening and the second gas-solid separating device (9) bottom solid outlet be connected；The heat carrier conveying dress
The thermal cyclic carrier discharging opening for putting (8) bottom is connected with pyrolysis reactor (3) upper feed inlet.
5. system according to claim 2, it is characterised in that the burning also includes returning charge with catalyst regeneration units and filled
Put (6) and heat carrier conveying device (8), the upper feed inlet of the material-returning device (6) simultaneously with pyrolysis reactor (3) bottom
Pyrolysis char discharging opening and the solid product discharging opening of the first gas-solid separating device (4) bottom are connected；The material-returning device (6)
The discharging opening of bottom or sidepiece is connected with the mixed material entrance of combustion reactor (7) lower sides；
The thermal cyclic carrier charging aperture on the top of the heat carrier conveying device (8) respectively with combustion reactor (7) upper portion side wall
Thermal cyclic carrier discharging opening and the second gas-solid separating device (9) bottom solid outlet be connected；The heat carrier conveying dress
The thermal cyclic carrier discharging opening for putting (8) bottom is connected with pyrolysis reactor (3) upper feed inlet.
6. according to any described systems of claim 1-5, it is characterised in that the preprocessor (1) uses reacting in rotary kiln
It is any in device, spiral drop flow reactor or blade stirring formula reactor with deflection plate；The pyrolysis reactor (3) is adopted
With helical reactors or piece-picking type reactor；The combustion reactor (7) is using circulating fluid bed reactor, fluidized bed furnace reactor
Or it is any in gasoline stock.
7. a kind of adhesive sticker pyrolysis of waste trans-utilization method based on system described in claim 1, comprises the following steps：
1) the adhesive sticker waste materials particle after will be broken sends into preprocessor (1), with the gas-phase heating medium counter flow being passed through
Contact, raw material is sufficiently heated；
2) pretreated material enters pyrolysis reactor (3), is sufficiently mixed with the grey heat carrier of high temperature combustion of input, and in combustion ash
Quick catalysis pyrolysis is carried out in the presence of middle calcium oxide, pyrolysis char and pyrolysis oil gas mix products is produced；
3) pyrolysis char for producing pyrolysis reactor (3) is delivered to combustion reactor (7), with being passed through by combustion reactor bottom
Combustion-supporting gas burn；Burnt in combustion reactor generation flue gas entrained solids fine ash particle enter the second gas solid separation
Device (9), the solid fine ash particle produced after separation returns to pyrolysis reactor (3)；The high temperature produced in combustion reactor (7)
Combustion ash is delivered to pyrolysis reactor (3), and thermal source and calcium based catalysts are provided for pyrolytic process as active thermal cyclic carrier.
8. method according to claim 7, it is characterised in that preprocessor (1) the connection milk of lime absorption cell (2),
The step 1) in raw material be sufficiently heated, decompose in raw material chlorine-bearing compound and produce hydrogen chloride, part organic matter is pyrolyzed
A small amount of pyrolysis gas and water vapour are produced, chlorine contained exhaust gas is formed under heating medium flow field entrainment effect, and enter milk of lime absorption cell
(2)。
9. the method according to claim 7 or 8, it is characterised in that the upper part discharge port of the pyrolysis reactor (3) and the
The charging aperture connection of one gas-solid separating device (4), gaseous product discharging opening and the gas-liquid separation of the first gas-solid separating device (4) are filled
Put the charging aperture connection of (5)；
Step 2) in, the pyrolysis oil gas mix products that the pyrolysis reactor (3) produces are through the first gas-solid separating device (4) and gas
Liquid separating apparatus (5) is separated, and respectively obtains pyrolysis oil and pyrolysis gas product；
Sent through the isolated fine grained of the first gas-solid separating device (4) together with the pyrolysis char that pyrolysis reactor (3) is produced
Enter combustion reactor (7).
10. according to any described methods of claim 7-9, it is characterised in that step 3) through the second gas-solid separating device (9) place
Flue gas after reason is used as gas-phase heating medium into preprocessor (1).
11. the method according to claim 7-9, it is characterised in that it is described it is broken after adhesive sticker waste materials particle
Grain size be 0.1~10cm.
12. the method according to claim 7-9, it is characterised in that the heating medium is that pyrolysis char burns what is produced
In heat smoke, or the steam produced for heat smoke heat exchange, or the steam produced for the heat exchange of pyrolysis gas-phase product condensation process
One or more.
13. the method according to claim 7-9, it is characterised in that the combustion-supporting gas is air, or oxygen, or oxygen rich air
Any of body.
14. the method according to claim 7-9, it is characterised in that the temperature in the preprocessor (1) is 150~350
℃；Temperature in the pyrolysis reactor (3) is 300~750 DEG C；Temperature in the combustion reactor (7) is 700~1000
℃。
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| CN114479952A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Biomass hydrogen production heat carrier and preparation method and application thereof |
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