CN104479722A - Continuous segmented cracking equipment and technology used for waste and old tyres and capable of preventing generation of dioxin - Google Patents
Continuous segmented cracking equipment and technology used for waste and old tyres and capable of preventing generation of dioxin Download PDFInfo
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- CN104479722A CN104479722A CN201410612344.8A CN201410612344A CN104479722A CN 104479722 A CN104479722 A CN 104479722A CN 201410612344 A CN201410612344 A CN 201410612344A CN 104479722 A CN104479722 A CN 104479722A
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/482—Preparation from used rubber products, e.g. tyres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- 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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a continuous segmented cracking equipment and a technology used for waste and old tyres and capable of preventing generation of dioxin. The equipment comprises a raw material bin, a mixing feeding screw conveyor, a preheating furnace, a continuous thermal cracking device and an oil gas recovery device; the raw material bin is successively connected with the mixing feeding screw conveyor, the preheating furnace and the continuous cracking device; the preheating furnace successively comprises a heating segment, a sealing segment, a forward pushing segment and a discharging segment along the flowing direction of a raw material, the heating segment and the forward pushing segment are both provided with a screw pusher, and the screwing direction of the screw pushers in the heating segment and in the forward pushing segment are same, and the sealing segment is not provided with a screw pusher; and the continuous cracking device successively comprises a first cracking unit with the heating temperature of 340-360 DEG C, a second cracking unit with the heating temperature of 440-460 DEG C and a third cracking unit with the heating temperature of 540-560 DEG C. The equipment and the technology are capable of effectively preventing generation of dioxin in the process of processing waste and old tyres, improving the activity and the quality of carbon black, and realizing continuous cracking production of waste and old tyres.
Description
Technical field
The present invention relates to junked tire processing technology field, be specifically related to a kind of prevent dioxin from producing junked tire contiguous segmentation cracking apparatus and technique.
Background technology
The thermo-cracking of junked tire is damaged tire comprehensive utilization, last one committed step turned waste into wealth.For a long time, be subject to various circles of society and pay close attention to greatly, a lot of researchist is for this has been large quantifier elimination and cut-and-try work.But still do not form a desirable mass-producing, industrialization, serialization and meet environmental requirement for various reasons so far, and production line feasible economically.Up to the present, existingly can carry out the cracking of quantity-produced pyrolysis oven to junked tire and bias toward oil separating process, the carbon black mass finally obtained is unsatisfactory, and although the pyrolysis oven of batch production can make the performance of over-all properties close to N660 of pyrolytic carbon black, but due to can not continuous seepage be carried out, still there is energy dissipation, environmental pollution and high in cost of production problem.
In addition, intermittent type revolution pyrolyzer and the continuous rotary pyrolyzer of adopting carries out thermo-cracking to realize the recycling of junked tire to junked tire more at present, but when adopting aforesaid device to carry out cracking to junked tire, because fill process inevitably brings partial air into, the intermediate product (as benzene, chlorine, chlorinated benzene etc.) produced can be reacted with the air one brought into give birth to into dioxin in tire pyrolysis process.Er dioxin is the chlorine-containing organic compounds linking 2 phenyl ring containing 2 or 1 oxygen, there is stronger toxicity, to environment and harm very big.
Therefore, find a kind of pyrolytic reaction being conducive to various rubber constituent in junked tire to carry out continuously, fully, be conducive to the activity and the quality that improve carbon black, and the junked tire treatment facility that can effectively prevent dioxin from producing and technique become this area problem urgently to be resolved hurrily simultaneously.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of junked tire contiguous segmentation cracking apparatus preventing dioxin from producing, the seal section of this junked tire contiguous segmentation cracking apparatus by arranging in preheating oven without screw impeller, can air be effectively stoped to enter pyrolyzer, prevent the generation of junked tire treating processes Zhong dioxin, segmentation cracking is carried out to junked tire simultaneously, improve activity and the quality of carbon black, achieve the continuous seepage of junked tire cracking with less energy-consumption.
Another object of the present invention is to provide a kind of junked tire contiguous segmentation cracking technology preventing dioxin from producing.
For achieving the above object, the invention provides a kind of junked tire contiguous segmentation cracking apparatus preventing dioxin from producing, this junked tire contiguous segmentation cracking apparatus comprises raw material cabin, mixing reinforced spiral conveyer, preheating oven, continuous cracking device, vacuum extractor and device for recovering oil and gas, and wherein said raw material cabin connects mixing reinforced spiral conveyer, preheating oven and continuous cracking device successively;
Described preheating oven comprises heating zone, seal section, forward propelling section and blanking section successively from raw material flow direction, described heating zone and described forward advance in section and arrange screw impeller respectively, and described heating zone and described forward advance the hand of spiral of the screw impeller in section identical, do not arrange screw impeller in described seal section;
Described continuous cracking device comprises the first cracking unit, the second cracking unit and the 3rd cracking unit that connect successively; The Heating temperature of wherein said first cracking unit is 340-360 DEG C, for the natural rubber cracking in the material that obtained by preheating oven; The Heating temperature of described second cracking unit is 440-460 DEG C, for the cis-1,4-polybutadiene rubber in material that the first cracking unit is obtained and styrene-butadiene rubber(SBR) cracking, the Heating temperature of described 3rd cracking unit is 540-560 DEG C, for the carbonaceous sediment cracking of the carbon blacksurface in the material that obtained by the second cracking unit;
Described vacuum extractor is communicated with preheating oven and continuous cracking device respectively, for vacuumizing the first cracking unit of preheating oven and continuous cracking device, the second cracking unit and the 3rd cracking unit, to extract the gas produced in each unit of preheating oven and continuous cracking device respectively;
Described device for recovering oil and gas is used for recycling the gas that described vacuum extractor extracts.
In the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention, the temperature of described preheating oven is 230-250 DEG C, preferably 240 DEG C, for by the soft plastic state of pre-for junked tire material thermosetting;
Preferably, described preheating oven arranges far-infrared heating layer.
In the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention, the heating zone of described preheating oven, seal section, forward advance the length ratio of section and blanking section to be 17-21:0.5-1.5:0.5-3:0.5-3, preferred 19:1:1.5:1.5;
Preferably, the end of described preheating oven arranges reverse propulsion section, and described reverse propulsion section is adjacent with described blanking section, and is provided with screw impeller, and described reverse propulsion section and described forward advance the hand of spiral of the screw impeller in section contrary;
Preferably, the heating zone of described preheating oven, seal section, forward advance the length ratio of section, blanking section and reverse propulsion section to be 17-21:0.5-1.5:0.5-3:0.5-3:0.5-1.5, preferred 19:1:1.5:1.5:1.
In the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention, described raw material cabin with described mix to feed in raw material between spiral conveyer, flexible star type be set seal blanking device, gusset is provided with in described flexible star type sealing blanking device, the end that described gusset is engaging with the shell that flexible star type seals blanking device adopts flexible materials to make, and preferably adopts tetrafluoroethylene to make;
Preferably, the heating zone end of described preheating oven arranges oil gas vent;
Preferably, the described mixing spiral conveyer that feeds in raw material arranges catalyst inlet and reuse high temperature carbon black entrance, the high temperature carbon black produced after being respectively used to add junked tire cracking catalyzer and junked tire cracking.
In the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention, the Heating temperature of described first cracking unit is 350 DEG C; The Heating temperature of described second cracking unit is 450 DEG C; The Heating temperature of described 3rd cracking unit is 550 DEG C;
Preferably, described first cracking unit is set to the average heating rate of 8-12 DEG C/min, and more preferably the average heating rate of 10 DEG C/min is warming up to 340-360 DEG C;
Preferably, described second cracking unit is set to the average heating rate of 8-12 DEG C/min, and more preferably the average heating rate of 10 DEG C/min is warming up to 440-460 DEG C;
Preferably, described 3rd cracking unit is set to the average heating rate of 8-12 DEG C/min, and more preferably the average heating rate of 10 DEG C/min is warming up to 540-560 DEG C.
Preferably, the vacuum tightness that described vacuum extractor reaches is-0.5 ± 0.3KPa, is preferably-0.5 ± 0.1KPa.
The present invention further provides a kind of junked tire contiguous segmentation cracking technology preventing dioxin from producing, in described junked tire contiguous segmentation cracking technology, adopt junked tire contiguous segmentation cracking apparatus as above to carry out cracking to junked tire.
The junked tire contiguous segmentation cracking technology preventing dioxin from producing of the present invention comprises:
Step a: little blob of viscose junked tire being processed as steel wire, drops into raw material cabin, enters the reinforced spiral conveyer of mixing subsequently;
Step b: by the junked tire mass transport in reinforced for mixing spiral conveyer to preheating oven, by soft for pre-for junked tire material thermosetting plastic state material in preheating oven, and the gas adopting vacuum extractor to extract to produce in warm;
Step c: carry out cracking by the soft plastic state mass transport to continuous cracking device formed in preheating oven, and the gas adopting vacuum extractor to extract to produce in cracking process;
Steps d: adopt device for recovering oil and gas to recycle the gas extracted in step b and step c.
The junked tire contiguous segmentation cracking technology preventing dioxin from producing as above, in described step b, by junked tire material preheating 15-25 minute at 230-250 DEG C in preheating oven, form soft plastic state material, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas of generation;
Preferably, in described step b, by junked tire material preheating 15-25 minute at 240 DEG C in preheating oven, form soft plastic state material;
More preferably, in described step b, by the preheating 20 minutes at 240 DEG C of junked tire material in preheating oven, form soft plastic state material.
The junked tire contiguous segmentation cracking technology preventing dioxin from producing as above, described step c comprises:
Step c1: by the soft plastic state mass transport that formed in preheating oven to the first cracking unit of continuous cracking device, material is made to be warming up to 340-360 DEG C in the first cracking unit, and 8-12 minute is heated at 340-360 DEG C, make natural rubber cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas produced in cracking process
Step c2: by mass transport to the second cracking unit in the first cracking unit, material is made to be warming up to 440-460 DEG C in the second cracking unit, and 8-12 minute is heated at 440-460 DEG C, make cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR) cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas produced in cracking process
Step c3: by the mass transport in the second cracking unit to the 3rd cracking unit, material is made to be warming up to 540-560 DEG C in the 3rd cracking unit, and 8-12 minute is heated at 540-560 DEG C, make the carbonaceous sediment cracking of carbon blacksurface, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas produced in cracking process.
The junked tire contiguous segmentation cracking technology preventing dioxin from producing as above, in described step c1, make material with the average heating rate of 8-12 DEG C/min in the first cracking unit, more preferably the average heating rate of 10 DEG C/min is warming up to 340-360 DEG C; Preferably, in described step c1, make material heat 8-12 minute at 350 DEG C, more preferably, material is heated 10 minutes at 350 DEG C;
In described step c2, make material with the average heating rate of 8-12 DEG C/min in the second cracking unit, more preferably the average heating rate of 10 DEG C/min is warming up to 440-460 DEG C; Preferably, make material heat 8-12 minute at 450 DEG C, more preferably, material is heated 10 minutes at 450 DEG C;
In described step c3, make material with the average heating rate of 8-12 DEG C/min in the 3rd cracking unit, more preferably the average heating rate of 10 DEG C/min is warming up to 540-560 DEG C; Preferably, make material heat 8-12 minute at 550 DEG C, more preferably, material is heated 10 minutes at 550 DEG C.
The junked tire contiguous segmentation cracking technology preventing dioxin from producing as above, in described step b, by the preheating 20 minutes at 240 DEG C of junked tire material in preheating oven, form soft plastic state material, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas of generation; And described step c comprises:
Step c1: by the soft plastic state mass transport that formed in preheating oven to the first cracking unit of continuous cracking device, material is made to be warming up to 350 DEG C with the average heating rate of 10 DEG C/min in the first cracking unit, and heat 10 minutes at 350 DEG C, make natural rubber cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas produced in cracking process
Step c2: by mass transport to the second cracking unit in the first cracking unit, material is made to be warming up to 450 DEG C with the average heating rate of 10 DEG C/min in the second cracking unit, and heat 10 minutes at 450 DEG C, make cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR) cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas produced in cracking process
Step c3: by the mass transport in the second cracking unit to the 3rd cracking unit, material is made to be warming up to 550 DEG C with the average heating rate of 10 DEG C/min in the 3rd cracking unit, and heat 10 minutes at 550 DEG C, make the carbonaceous sediment cracking of carbon blacksurface, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas produced in cracking process.
Great many of experiments confirms that the pyrolytic reaction of junked tire is a very complicated chemical reaction process, and after temperature reaches the cracking temperature of certain rubber, this kind of rubber molecule decomposes, and with second pyrolysis and the multiple reaction such as coking, polymerization.Because most of Tire production producer generally all at least uses three kinds of rubber such as NR (natural rubber), BR (cis-1,4-polybutadiene rubber) and SBR (styrene-butadiene rubber(SBR)) when producing, and these three kinds of rubber respectively have its optimum pyrolysis temperature, and the highest and minimum pyrolysis temperature difference reaches more than 50 DEG C.In order to make various rubber constituent in junked tire fully carry out pyrolytic reaction, realize the most effective comprehensive utilization continuously of junked tire.The present invention finds after deliberation, at the temperature that certain is applicable to, makes certain rubber cracking, and the low molecular hydrocarbon that its cracking produces is extracted out rapidly, depart from environment, can effectively prevent them from regrouping, coking or cover the surface of carbon black grain, namely form so-called carbonaceous sediment.Under this thought guidance, have devised junked tire contiguous segmentation cracking apparatus of the present invention and technique.
Dioxin is the chlorine-containing organic compounds linking 2 phenyl ring containing 2 or 1 oxygen, has multiple isomer, but all containing aerobic (O) in various isomer.The temperature that dioxin generates is 250-550 DEG C (optimal temperature is 300-500 DEG C), and its precursor comprises HCl, Cl
2, O
2and all kinds of chlorinated benzene etc.The precursor producing dioxin in junked tire cracking process is mainly derived from the intermediate product produced in tire pyrolysis process, as benzene, chlorine and chlorinated benzene etc., due in the various isomer of dioxin all containing aerobic (O), therefore, if make junked tire cracking in the environment of anoxic, the generation of dioxin just effectively can be stoped.Based on this, the seal section of the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention by arranging in preheating oven without screw impeller, make the material being full of soft plastic state in seal section, formed closely air-locked " sealed wall ", thus can effectively stop air to enter continuous cracking device, make material cracking in the environment of anoxic, and then efficiently avoid the generation of junked tire treating processes Zhong dioxin.
Compared with existing junked tire treatment facility and technique, junked tire contiguous segmentation cracking apparatus of the present invention and technique at least have the following advantages:
One, adopt continuous cracking device to carry out segmentation cracking to junked tire in junked tire contiguous segmentation cracking apparatus of the present invention, this continuous cracking device comprises: for the first cracking unit of cracking natural rubber; For the second cracking unit of cracking cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR); For removing the carbonaceous sediment of carbon blacksurface, improve the activity of carbon black and the 3rd cracking unit of quality; Vacuum extractor makes cracking process be negative pressure state in addition, and to extract the gas produced in each unit in time, the low molecular hydrocarbon gas prevented regroups, coking or cover the surface of carbon black grain, forms carbonaceous sediment; By thermal cracking processes is carried out two-stage temperature control, can decompose fully the natural rubber in tire, cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR), especially in the 3rd cracking unit, set temperature is: 540-560 DEG C, effectively can remove the carbonaceous sediment of carbon blacksurface, improve activity and the quality of carbon black, can also reclaim fully " oil " in tire simultaneously, thus have effectively achieved the recycling of pyrolytic carbon black, and prevent equipment coking, be conducive to save energy and continuous seepage;
Two, junked tire material is added the material of the soft plastic state of thermosetting by the present invention in preheating oven, by arranging the seal section without screw impeller in preheating oven, the material of soft plastic state is made to be full of seal section, formed closely air-locked " sealed wall ", thus can effectively stop air to enter pyrolyzer, junked tire is enable to carry out cracking under the environment of anoxic, thus can effectively prevent the generation of junked tire cracking process Zhong dioxin from (owing to carrying out cracking under the environment of anoxic, also contributing to reducing SO
2generation); In addition, the present invention, by the length ratio reasonably arranging heating zone in preheating oven, seal section, forward advance section, blanking section and reverse propulsion section, can realize air-isolation well, avoids dioxin (and SO
2deng pollution gas) generation, be conducive to again promote material, make it enter the cracking of contiguous segmentation pyrocrack furnace smoothly;
Three, the present invention arranges flexible star type sealing blanking device further between raw material cabin and the reinforced spiral conveyer of mixing, the gusset of this flexible star type sealing blanking device adopts flexible materials to make at the end engaged with shell, air can be completely cut off preferably, prevent outside air from entering the reinforced spiral conveyer of mixing, when avoiding adopting common rigidity blanking device, and the defect that cause partial air enter poor due to blanking device stopping property, thus contribute to the generation reducing dioxin.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is the schematic diagram of the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention.
Fig. 2 is the diagrammatic cross-section of flexible star type sealing blanking device in the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention.
Description of reference numerals
1 raw material cabin
11 raw material cabin entrances
2 sealing blanking devices
21 shells
22 gussets
221 flexible sealing materials
222 springs
23 axles
The reinforced spiral conveyer of 3 mixing
31 catalyst inlets
32 reuse high temperature carbon black entrances
4 preheating ovens
41 heating zones
42 seal sections
43 forwards advance section
44 blanking sections
45 reverse propulsion sections
41', 43', 45' screw impeller
46 zones of heating
47 oil gas vents
5 continuous cracking devices
51 first cracking unit
52 second cracking unit
53 the 3rd cracking unit
6 device for recovering oil and gas
7 vacuum extractors
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment provided only in order to illustrate the present invention, instead of in order to limit the scope of the invention.
As shown in Figure 1, the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention comprises raw material cabin 1, mixing reinforced spiral conveyer 3, preheating oven 4, continuous cracking device 5, device for recovering oil and gas 6 and vacuum extractor 7, and wherein raw material cabin 1 connects mixing reinforced spiral conveyer 3, preheating oven 4 and continuous cracking device 5 successively.Raw material cabin 1 seals blanking device 2 with mixing to arrange between reinforced spiral conveyer 3.Raw material cabin 1 is arranged raw material cabin entrance 11, for throwing in junked tire raw material.The reinforced spiral conveyer 3 of mixing arranges catalyst inlet 31 and reuse high temperature carbon black entrance 32, the high temperature carbon black produced after being respectively used to add junked tire cracking catalyzer and junked tire cracking, by the high temperature carbon black produced after the cracking of interpolation junked tire, the mutual felt jam preheating oven 4 of material being heated to soft plastic state can be prevented on the one hand, the waste heat that can make full use of the high temperature carbon black of recovery on the other hand heats material, realizes the recycle of energy.Preheating oven 4 comprises heating zone 41, seal section 42, forward propelling section 43, blanking section 44 and reverse propulsion section 45 successively from raw material flow direction, wherein heating zone 41, forward advance in section 43 and reverse propulsion section 45 and arrange screw impeller 41', 43' and 45' respectively, it act as auger material and advances, in seal section 42, screw impeller is not set, wherein the hand of spiral of screw impeller 41' and 43' is identical, and the hand of spiral of screw impeller 45' is contrary with the hand of spiral of screw impeller 41' and 43'.Heating zone 41, seal section 42, forward advances section 43, the length of blanking section 44 and reverse propulsion section 45 is respectively s1 (between the end of preheating oven 4 and A), s2 (between A and B), s3 (between B and C), s4 (between C and D) and s5 (between the end of D and preheating oven 4), wherein s1, s2, s3, the ratio of s4 and s5 is 17-21:0.5-1.5:0.5-3:0.5-3:0.5-1.5, preferred 19:1:1.5:1.5:1, by arranging s1, s2, s3, ratio between s4 and s5, can air-isolation well, avoid the generation of dioxin, be conducive to again promoting material, it is made to enter continuous cracking device 5 cracking smoothly.Heating zone 41 arranges zone of heating 46, preferred far-infrared heating layer.The temperature of preheating oven 4 is set to 230-250 DEG C, preferably 240 DEG C, and the generation temperature due to dioxin is 250-550 DEG C, and therefore, junked tire raw material can't produce dioxin in preheating oven 4 after heating zone 41 heats.In fact, after material enters preheating oven 4 from the reinforced spiral conveyer 3 of mixing, first push by screw impeller 41' spiral and travel forward, and heated at the volley, when material is pushed to seal section 42 (A), material is made to lose the power of advance owing to there is no screw impeller in seal section 42, do not readvance, and pile up at seal section 42 place, and now material has been heated to be the material of soft plastic state, the material of this soft plastic state is cumulative at seal section 42 place, material below is constantly pushed away again, the material of soft plastic state is finally made to be full of seal section 42, formed closely air-locked " sealed wall ", " sealed wall " should can play the effect completely cutting off air well, thus avoid air to enter pyrolyzer.But along with material constantly pushes away below, " sealed wall " still can be pushed and move forward, enter forward subsequently and advance section 43, promoted forward by screw impeller 43', enter blanking section 44, enter continuous cracking device 5 subsequently, until cracking terminates, material is cracking in the environment of airtight anoxia completely, thus avoids the generation of dioxin in tyre spit solution preocess.
In addition, the easy felt jam preheating oven of material due to soft plastic state, more easily continuous cracking device is entered for making material, the hand of spiral of the screw impeller 45' in reverse propulsion section 45 is set to advance the direction of the screw impeller 43' in section 43 contrary with forward by the present invention, thus be more conducive to the material of soft plastic state being pushed to blanking section and then entering continuous cracking device (it should be noted that herein, reverse propulsion section 45 and wherein screw impeller 45' just make material enter continuous cracking device for being more convenient for and arrange, and it is nonessential, reverse propulsion section 45 can be set according to practical situation yet, now blanking section 44 is arranged on preheating oven 4 end), in addition, at the end of heating zone 41, oil gas vent 47 is set, this oil gas vent 47 is set to vacuum outlet, in time the oil gas that junked tire raw material produces in pyrolytic process can be taken away.
The star-like sealing blanking device of sealing blanking device 2 preferred flexible of the present invention, as shown in Figure 2, flexible star type sealing blanking device of the present invention comprises shell 21, gusset 22 and axle 23, the internal space that wherein flexible star type is sealed blanking device by gusset 22 separates, gusset 22 comprises flexible sealing material 221 and spring 222, wherein flexible sealing material 221 can realize good joint with shell 21, make flexible star type seal blanking device and there is good stopping property, air can be completely cut off preferably, prevent outside air from entering the reinforced spiral conveyer 3 of mixing, described flexible sealing material 221 is preferably tetrafluoroethylene.In Fig. 2, the gusset quantity of flexible star type sealing blanking device just schematically, does not represent real quantity, can select according to practical situation in addition.
Continuous cracking device 5 of the present invention comprises the first cracking unit 51, the second cracking unit 52 and the 3rd cracking unit 53 that connect successively, the Heating temperature of described first cracking unit 51 is 340-360 DEG C, preferably 350 DEG C, for the natural rubber cracking in material that preheating oven 4 is obtained; The Heating temperature of described second cracking unit 52 is 440-460 DEG C, preferably 450 DEG C, for the cis-1,4-polybutadiene rubber in material that the first cracking unit 51 is obtained and styrene-butadiene rubber(SBR) cracking, the Heating temperature of described 3rd cracking unit 53 is 540-560 DEG C, preferably 550 DEG C, for the carbonaceous sediment cracking of the carbon blacksurface in material that the second cracking unit 52 is obtained, to improve activity and the quality of carbon black.
Vacuum extractor 7 is communicated with the first cracking unit 51, second cracking unit 52 of preheating oven 4 and continuous cracking device 5 and the second cracking unit 53 respectively, for vacuumizing each cracking unit of preheating oven 4 and continuous cracking device 5 respectively, to extract the gas produced in each cracking unit of preheating oven 4 and continuous cracking device 5.The gas extracted through vacuum extractor 7 enters device for recovering oil and gas 6, to recycle the oily substance in gas.
embodiment 1
The junked tire contiguous segmentation cracking apparatus (wherein the heating zone 41 of preheating oven 4, seal section 42, forward advance the length of section 43, blanking section 44 and reverse propulsion section 45 than being 19:1:1.5:1.5:1) preventing dioxin from producing shown in Fig. 1 is adopted to process junked tire material.First by the little blob of viscose of junked tire processing into about the steel wire of 1 ~ 2cm, then by incoming stock storehouse 1, feed(raw material)inlet 11, raw material enters the reinforced spiral conveyer 3 of mixing by sealing blanking device 22 subsequently, additionally by catalyst inlet 31 and the reuse high temperature carbon black entrance 32 of the reinforced spiral conveyer 3 of mixing, the high temperature carbon black produced after adding junked tire cracking catalyzer and junked tire cracking respectively, then material enters preheating oven 4, in preheating oven 4, material is heated about 20 minutes at 240 DEG C, material is made to become the material of soft plastic state, the material of this soft plastic state is pushed into seal section 42, formed closely air-locked " sealed wall ", after this enter forward and advance section 43, and promoted forward by screw impeller 43', enter blanking section 44, enter the first cracking unit 51 of continuous cracking device 5 subsequently, first material is warming up to 350 DEG C with the average heating rate of 10 DEG C/min in this unit, and about 10min is heated at 350 DEG C, material enters the second cracking unit 52 subsequently, and first material is warming up to 450 DEG C with the average heating rate of 10 DEG C/min by this unit, and heats about 10min at 450 DEG C, after this material enters the 3rd cracking unit 53, and first material is warming up to 550 DEG C with the average heating rate of 10 DEG C/min by this unit, and heats about 10min at 550 DEG C.Until cracking terminates, material is cracking in the environment of airtight anoxia completely, thus avoids the generation of dioxin in tyre spit solution preocess.In material preheating and cracking process, keep negative pressure (-0.5 ± 0.1KPa) basicly stable by vacuum extractor 7, to extract the gas produced in each unit of preheating oven 4 and continuous cracking device 5, the gas extracted enters device for recovering oil and gas 6, to recycle.The carbon black that material produces after continuous cracking device 5 cracking enters high temperature coarse carbon black bin, finally conventional method is adopted to carry out deep processing the coarse carbon black obtained, deep-processing process comprises: coarse carbon black is ground into the fine powder that particle diameter is less than 4 μm, adopt coupling agent (OL-AT1618) and stearic acid that fine powder is carried out activation modification again, granulation, and to be dried to water content be less than 1.5%, after screening, obtain the dustless carbon black that particle diameter is about 0.25-2.5mm.
The performance of the carbon black obtained by above-described embodiment 1 is tested, and result is as shown in table 1:
Table 1: carbon black performance test
As seen from Table 1, adopt of the present invention prevent dioxin from producing junked tire contiguous segmentation cracking apparatus and the specific surface area of carbon black that obtains of technique larger, impurity is less and intensity is higher, wherein iodine absorption value, N2 adsorption specific surface area and 300% stress at definite elongation are all far above the respective performances test value of N630 carbon black, and DBP value is suitable with N630 carbon black.Consolidated statement 1 data are known, the carbon black adopting the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing of the present invention to obtain close to or more than the over-all properties of N6 series carbon black, show to adopt of the present invention prevent dioxin from producing junked tire contiguous segmentation cracking apparatus and the carbon black that obtains of technique there is higher activity and quality.
Claims (12)
1. the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing, comprise raw material cabin, mixing reinforced spiral conveyer, preheating oven, continuous cracking device, vacuum extractor and device for recovering oil and gas, wherein said raw material cabin connects mixing reinforced spiral conveyer, preheating oven and continuous cracking device successively;
Described preheating oven comprises heating zone, seal section, forward propelling section and blanking section successively from raw material flow direction, described heating zone and described forward advance in section and arrange screw impeller respectively, and described heating zone and described forward advance the hand of spiral of the screw impeller in section identical, do not arrange screw impeller in described seal section;
Described continuous cracking device comprises the first cracking unit, the second cracking unit and the 3rd cracking unit that connect successively; The Heating temperature of wherein said first cracking unit is 340-360 DEG C, for the natural rubber cracking in the material that obtained by preheating oven; The Heating temperature of described second cracking unit is 440-460 DEG C, for the cis-1,4-polybutadiene rubber in material that the first cracking unit is obtained and styrene-butadiene rubber(SBR) cracking, the Heating temperature of described 3rd cracking unit is 540-560 DEG C, for the carbonaceous sediment cracking of the carbon blacksurface in the material that obtained by the second cracking unit;
Described vacuum extractor is communicated with preheating oven and continuous cracking device respectively, for vacuumizing the first cracking unit of preheating oven and continuous cracking device, the second cracking unit and the 3rd cracking unit, to extract the gas produced in each unit of preheating oven and continuous cracking device respectively;
Described device for recovering oil and gas is used for recycling the gas that described vacuum extractor extracts.
2. the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing according to claim 1, is characterized in that, the temperature of described preheating oven is 230-250 DEG C, preferably 240 DEG C, for by the soft plastic state of pre-for junked tire material thermosetting;
Preferably, described preheating oven arranges far-infrared heating layer.
3. the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing according to claim 1 and 2, it is characterized in that, the heating zone of described preheating oven, seal section, forward advance the length ratio of section and blanking section to be 17-21:0.5-1.5:0.5-3:0.5-3, preferred 19:1:1.5:1.5;
Preferably, the end of described preheating oven arranges reverse propulsion section, and described reverse propulsion section is adjacent with described blanking section, and is provided with screw impeller, and described reverse propulsion section and described forward advance the hand of spiral of the screw impeller in section contrary;
Preferably, the heating zone of described preheating oven, seal section, forward advance the length ratio of section, blanking section and reverse propulsion section to be 17-21:0.5-1.5:0.5-3:0.5-3:0.5-1.5, preferred 19:1:1.5:1.5:1.
4. the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing according to any one of claim 1-3, it is characterized in that, described raw material cabin with described mix to feed in raw material between spiral conveyer, flexible star type be set seal blanking device, gusset is provided with in described flexible star type sealing blanking device, the end that described gusset is engaging with the shell that flexible star type seals blanking device adopts flexible materials to make, and preferably adopts tetrafluoroethylene to make;
Preferably, the heating zone end of described preheating oven arranges oil gas vent;
Preferably, the described mixing spiral conveyer that feeds in raw material arranges catalyst inlet and reuse high temperature carbon black entrance, the high temperature carbon black produced after being respectively used to add junked tire cracking catalyzer and junked tire cracking.
5. the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing according to any one of claim 1-4, is characterized in that, the Heating temperature of described first cracking unit is 350 DEG C; The Heating temperature of described second cracking unit is 450 DEG C; The Heating temperature of described 3rd cracking unit is 550 DEG C;
Preferably, described first cracking unit is set to the average heating rate of 8-12 DEG C/min, and more preferably the average heating rate of 10 DEG C/min is warming up to 340-360 DEG C;
Preferably, described second cracking unit is set to the average heating rate of 8-12 DEG C/min, and more preferably the average heating rate of 10 DEG C/min is warming up to 440-460 DEG C;
Preferably, described 3rd cracking unit is set to the average heating rate of 8-12 DEG C/min, and more preferably the average heating rate of 10 DEG C/min is warming up to 540-560 DEG C.
6. the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing according to any one of claim 1-5, it is characterized in that, the vacuum tightness that described vacuum extractor reaches is-0.5 ± 0.3KPa, is preferably-0.5 ± 0.1KPa.
7. the junked tire contiguous segmentation cracking technology preventing dioxin from producing, adopts the junked tire contiguous segmentation cracking apparatus preventing dioxin from producing according to any one of claim 1-6 to carry out cracking to junked tire in described junked tire treatment process.
8. the junked tire contiguous segmentation cracking technology preventing dioxin from producing according to claim 7, is characterized in that, described junked tire contiguous segmentation cracking technology comprises:
Step a: little blob of viscose junked tire being processed as steel wire, drops into raw material cabin, enters the reinforced spiral conveyer of mixing subsequently;
Step b: by the junked tire mass transport in reinforced for mixing spiral conveyer to preheating oven, by soft for pre-for junked tire material thermosetting plastic state material in preheating oven, and the gas adopting vacuum extractor to extract to produce in warm;
Step c: carry out cracking by the soft plastic state mass transport to continuous cracking device formed in preheating oven, and the gas adopting vacuum extractor to extract to produce in cracking process;
Steps d: adopt device for recovering oil and gas to recycle the gas extracted in step b and step c.
9. the junked tire contiguous segmentation cracking technology preventing dioxin from producing according to claim 8, it is characterized in that, in described step b, by junked tire material preheating 15-25 minute at 230-250 DEG C in preheating oven, form soft plastic state material, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas of generation;
Preferably, in described step b, by junked tire material preheating 15-25 minute at 240 DEG C in preheating oven, form soft plastic state material;
More preferably, in described step b, by the preheating 20 minutes at 240 DEG C of junked tire material in preheating oven, form soft plastic state material.
10. the junked tire contiguous segmentation cracking technology preventing dioxin from producing according to claim 8 or claim 9, it is characterized in that, described step c comprises:
Step c1: by the soft plastic state mass transport that formed in preheating oven to the first cracking unit of continuous cracking device, material is made to be warming up to 340-360 DEG C in the first cracking unit, and 8-12 minute is heated at 340-360 DEG C, make natural rubber cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas produced in cracking process
Step c2: by mass transport to the second cracking unit in the first cracking unit, material is made to be warming up to 440-460 DEG C in the second cracking unit, and 8-12 minute is heated at 440-460 DEG C, make cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR) cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas produced in cracking process
Step c3: by the mass transport in the second cracking unit to the 3rd cracking unit, material is made to be warming up to 540-560 DEG C in the 3rd cracking unit, and 8-12 minute is heated at 540-560 DEG C, make the carbonaceous sediment cracking of carbon blacksurface, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.3KPa, extract the gas produced in cracking process.
The 11. junked tire contiguous segmentation cracking technologies preventing dioxin from producing according to claim 10, it is characterized in that, in described step c1, make material with the average heating rate of 8-12 DEG C/min in the first cracking unit, more preferably the average heating rate of 10 DEG C/min is warming up to 340-360 DEG C; Preferably, in described step c1, make material heat 8-12 minute at 350 DEG C, more preferably, material is heated 10 minutes at 350 DEG C;
In described step c2, make material with the average heating rate of 8-12 DEG C/min in the second cracking unit, more preferably the average heating rate of 10 DEG C/min is warming up to 440-460 DEG C; Preferably, make material heat 8-12 minute at 450 DEG C, more preferably, material is heated 10 minutes at 450 DEG C;
In described step c3, make material with the average heating rate of 8-12 DEG C/min in the 3rd cracking unit, more preferably the average heating rate of 10 DEG C/min is warming up to 540-560 DEG C; Preferably, make material heat 8-12 minute at 550 DEG C, more preferably, material is heated 10 minutes at 550 DEG C.
12. junked tire contiguous segmentation cracking technologies preventing dioxin from producing according to Claim 8 according to any one of-11, it is characterized in that, in described step b, by the preheating 20 minutes at 240 DEG C of junked tire material in preheating oven, form soft plastic state material, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas of generation; And described step c comprises:
Step c1: by the soft plastic state mass transport that formed in preheating oven to the first cracking unit of continuous cracking device, material is made to be warming up to 350 DEG C with the average heating rate of 10 DEG C/min in the first cracking unit, and heat 10 minutes at 350 DEG C, make natural rubber cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas produced in cracking process
Step c2: by mass transport to the second cracking unit in the first cracking unit, material is made to be warming up to 450 DEG C with the average heating rate of 10 DEG C/min in the second cracking unit, and heat 10 minutes at 450 DEG C, make cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR) cracking, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas produced in cracking process
Step c3: by the mass transport in the second cracking unit to the 3rd cracking unit, material is made to be warming up to 550 DEG C with the average heating rate of 10 DEG C/min in the 3rd cracking unit, and heat 10 minutes at 550 DEG C, make the carbonaceous sediment cracking of carbon blacksurface, and adopt vacuum extractor under vacuum tightness is-0.5 ± 0.1KPa, extract the gas produced in cracking process.
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| CN105331378A (en) * | 2015-10-28 | 2016-02-17 | 贵州安泰再生资源科技有限公司 | Method of comprehensively utilizing junked tire subjected to pyrolysis |
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| CN105331378B (en) * | 2015-10-28 | 2017-10-03 | 贵州安泰再生资源科技有限公司 | A kind of junked tire is pyrolyzed method of comprehensive utilization |
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| AU2017371717B2 (en) * | 2016-12-09 | 2022-10-06 | Keshi Technologies Pty Ltd | Process for the thermal degradation of rubber containing waste |
| US11591521B2 (en) | 2016-12-09 | 2023-02-28 | Keshi Technologies Pty Ltd | Hermetically sealed flow-through reactor for non-oxidative thermal degradation of a rubber containing waste |
| US11591522B2 (en) | 2016-12-09 | 2023-02-28 | Keshi Technologies Pty Ltd | Process for the thermal degradation of rubber containing waste |
| CN106916601A (en) * | 2017-03-29 | 2017-07-04 | 山东铂铠环保科技有限公司 | A kind of apparatus and method of the junked tire pyrolysis low ash content low-sulfur carbon black of production |
| CN108722320A (en) * | 2018-06-08 | 2018-11-02 | 国宏中晶（北京）科技发展有限公司 | A kind of multiple batches of catalyst adding set and method of waste tire |
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| CN108686586B (en) * | 2018-07-27 | 2023-08-08 | 青岛伊克斯达智能装备有限公司 | Whole tire feeding device and feeding method for thermal cracking of waste tires |
| CN111196931A (en) * | 2019-10-08 | 2020-05-26 | 北京星和众工设备技术股份有限公司 | Process method and device for controlled pyrolysis of organic solid waste |
| CN111704923A (en) * | 2020-06-22 | 2020-09-25 | 北京克林泰尔环保科技有限公司 | Cracking method of tire rubber for inhibiting generation of dioxin |
| WO2022202698A1 (en) * | 2021-03-22 | 2022-09-29 | 横浜ゴム株式会社 | Rubber composition for tire, and tire |
| JP2022146475A (en) * | 2021-03-22 | 2022-10-05 | 横浜ゴム株式会社 | Tire rubber composition and tire |
| CN113881452A (en) * | 2021-11-09 | 2022-01-04 | 山西能丰再生物资综合利用有限公司 | Efficient sectional type continuous cracking device and process for waste tires |
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