CN106635115A - Method for efficiently and cleanly preparing oil through mixed waste plastic garbage and hydrothermal reaction system - Google Patents
Method for efficiently and cleanly preparing oil through mixed waste plastic garbage and hydrothermal reaction system Download PDFInfo
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- CN106635115A CN106635115A CN201611176700.1A CN201611176700A CN106635115A CN 106635115 A CN106635115 A CN 106635115A CN 201611176700 A CN201611176700 A CN 201611176700A CN 106635115 A CN106635115 A CN 106635115A
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- waste plastic
- mixed waste
- rubbish
- hydrothermal
- hydrothermal reactor
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention provides a method for efficiently and cleanly preparing oil through mixed waste plastic garbage and a hydrothermal reaction system. The method comprises the steps that under the conditions that the temperature ranges from 160 DEG C to 300 DEG C and the pressure ranges from 20 bar to 220 bar, an alkaline water solution is used for carrying out pyrohydrolysis treatment on the mixed waste plastic garbage; the mixed waste plastic garbage contains one or more of PE, PP and PS, and PET, and the mixed waste plastic garbage can selectively comprise PVC; a water phase and a solid phase in a material obtained after hydro-thermal treatment are separated, and the solid phase obtained after separation is subjected to oil preparation. The negative influence of the PET and PVC in mixed waste plastic on the quality of the oil is avoided, the oil can be prepared efficiently and cleanly, a product, such as TA powder or particles and PS reprocessed plastic, with high additional value can be produced, organic matter in screened materials can also be utilized for anaerobic fermentation, the economical efficiency of this type of projects is improved, and meanwhile better circular using of resources is achieved.
Description
Technical field
The method and hydro-thermal reaction system of mixed plastic rubbish high-efficiency cleaning liquefaction is the present invention relates to the use of, is belonged to rubbish and is returned
Receive process field.
Background technology
It is a long-term technical issues that need to address that the resource of rubbish is recycled, while be also one receiving much concern
Social concern.Waste plastics is an important component part of rubbish, and Volume of Waste Plastics is fluffy, occupy volume big, according to measuring and calculating,
The loose bulk density of waste plastics is 55～66kg/m in house refuse3.Rubbish containing waste plastics carries out being accounted for during landfill stabilization
With storage capacity, and because degradation speed is slow, have a strong impact on Landfill Stabilization Rate process；And when being burned, easily produce dioxin etc.
Severe pollutant.Prior art is present to the waste plastics in rubbish by sorting enrichment to improve the content of plastics, then to it
Carry out thermal cracking and produce method of the oil to realize waste plastics resource.Although however, both at home and abroad to this waste plastic garbage resource
Change mode had trial, but rarely had the separation and recovery plastic cracking liquefaction successful case from rubbish.Trace it to its cause, mainly from rubbish
The waste plastics of the recovery in rubbish is mixing, and composition is complicated, often the mixture of various plastics, usually PE, PP, PS, PET
With the mixture of PVC, between these plastics and waste plastics and the rubber, paper, fabric, the wood chip that wherein mix etc. are to mixed plastic
Crack characteristic, product distribution have extremely complex impact.
As described above, such as mixed plastic PE, PP, PS, the PET and PVC mixed plastic reclaimed from rubbish is directly carried out
Cracking liquefaction, the then fuel oil low quality for producing generates a large amount of acids mainly due to two component cracking of PET and PVC
Matter (hydrogen chloride and organic acid) and granular substance, are easily oxidized, and property is unstable, and the pyrolysis product ratio of PE, PP and PS plastics
More satisfactory, the product quality for all mixing cracking liquefaction is very poor.Using existing isolation technics, by PVC and PET and PE,
PP and PS point is opened, extremely difficult, and mainly due to Jing on mixed plastic the impurity such as grease, dirt and swill are often attached to,
So that common wet method density separation and electrostatic separation inefficiency, the classification rate of recovery of various plastics is low.Such as adopt a large amount of water
Cleaning, is sorted again after being dried, then can cause very high water consume and energy consumption, and mixing of branching away speckles with dirt
The PET and PVC of dirt is difficult to recycle.
In summary, this area is needed badly and develops a kind of method and system of utilization mixed waste plastic rubbish high-efficiency cleaning liquefaction
To carry out high efficiente callback utilization to mixed waste plastic.
The content of the invention
Present invention is primarily targeted at providing a kind of method of utilization mixed waste plastic junk-free liquefaction, the method energy
The fuel oil quality for enough preparing mixed plastic is high, while high value added product can be efficiently produced, while the three wastes are produced less.
It is still another object of the present invention to provide the system that a kind of pyrohydrolysis suitable for said method is processed.It is using this
System can be energy-efficient carry out methods described.
For achieving the above object, the present invention provides a kind of method of utilization mixed waste plastic junk-free liquefaction, the side
Method comprises the steps：
(1) temperature be 160～300 DEG C and pressure be 20～220bar (such as 30bar, 50bar, 100bar, 200bar
Deng) under conditions of, pyrohydrolysis process is carried out to mixed waste plastic rubbish using alkaline aqueous solution；
The mixed waste plastic rubbish contains one or more in PE, PP, PS, and PET, the selective mixed waste plastic
Rubbish may also include PVC；
It is preferred that the mixed waste plastic rubbish contains PE, PP, PS, PET and PVC；
(2) the water phase in the material after hydro-thermal process is separated with solid phase, isolated solid phase is carried out into liquefaction.
The use pyrohydrolysis reaction of the invention is processed mixed waste plastic rubbish, and it is by mixed waste plastic rubbish
PET in rubbish is converted into the product such as terephthalic acid (TPA) (TA) and ethylene glycol (EG) and enters water phase, and keeps PE, PP, and/or PS
Quality Deng plastics solid phase is unaffected, and when such as in mixed waste plastic rubbish containing PVC, pyrohydrolysis reaction turns the chlorine in PVC
Change, into water phase, produce not chloride intermediate product, the intermediate product also can together go system with the plastics such as PE, PP, and/or PS
Oil, it is to avoid impacts of the PET and/or PVC in mixed waste plastic rubbish to liquefaction.
Specific implementation method of the invention, in the method for the invention, the alkaline aqueous solution is selected from Ca (OH)2
The aqueous solution, Ba (OH)2One or more in the aqueous solution, the KOH aqueous solution, the NaOH aqueous solution and the CsOH aqueous solution, preferred NaOH
The aqueous solution, it is further preferred that the concentration of the alkaline aqueous solution is 0.3mol/L～1.7mol/L.
Specific embodiment of the invention, in the method for the invention, the alkaline aqueous solution mixes with described
The volume mass ratio of waste plastic garbage is 2～5L:1Kg.
Liquefaction of the present invention can refer to prior art and carry out, it is preferable that the liquefaction is cracking oil-producing, more preferably
Ground, it comprises the steps：
The heat scission reaction kettle that step (2) gained solid phase (mixed plastic) sends into isolation air (can be given by double helix
Material machine or other forms batcher, continous way or batch-type all can), at 380～460 DEG C (reaction temperature depend on mixing modeling
The ratio of material each component), it is reacted to be converted into cracked oil under molecular sieve catalyst (such as HSM5, Y-zeolite etc.) catalysis
(may generally be the reaction of 10min～1h hours, this depends on reactor types).Experiment shows by the high-quality of present invention conversion
Cracked oil, comply fully with bunker oil standard, when treatment scale is more than 50,000 tons/year, it is still further contemplated that increase fractionation
Facility, upgrading products are gasoline, light diesel fuel and marine diesel oil.
Specific embodiment of the invention, in the method for the invention, when containing in the mixed waste plastic rubbish
There is PS, and during PE and/or PP, opened the PS and PE in step (2) gained solid phase and/or PP point using density-sorting methods, use
PE and/or PP liquefactions, are granulated using PS.Because all types of plastic density is different, part (such as PE/PP of water can be lighter than
Deng mixed plastic) separate with the part (such as PS) for overweighting water, make PS produce the regenerated plastics particle of higher quality, to realize giving up
The resource of plastic garbage is recycled.The density-sorting methods can refer to prior art and carry out.
Specific embodiment of the invention, in the method for the invention, with water phase isolated in step (2)
In fining end be divided into raw material and prepare terephthalic acid powder or particle, reclaiming the waste water containing ethylene glycol after terephthalic acid (TPA) can follow
Ring utilizes (such as cleaning equipment or cleaning removal of impurities), then enters back into anaerobic system and produces natural pond.As it was previously stated, step of the present invention
PET has been recycled well, and the water phase clarified solution after decomposition can produce high-purity TA powder or particle.
Specific embodiment of the invention, in the method for the invention, by water phase isolated in step (2)
In muddy part through filtering and cake dewatering, by filter cake part (mainly organic matter, including stalk, wood chip, paper etc.) point
Separate out the waste water reusable edible (such as cleaning equipment or cleaning removal of impurities) for anaerobic methane production, separated.When in waste water
When the indexs such as COD are too high, into after sewerage process, purging system is recycling in.
After water phase is separated with solid phase in the present invention, stratification, its top is clarification part, and bottom is muddy part.
The present invention can very well recycle PET, and can produce high-purity TA powder or particle, PS regenerated plastics particles etc.
High value added product, at the same time, when when containing PVC, PVC will be converted simultaneously, wherein there is cleavage reaction, by contained by PVC
Chlorine element convert, almost all enter water phase so that after conversion solid product be used for liquefaction when, such as thermal cracking oil-producing when, almost
No longer produce hydrogen chloride, and the quality of oil product is preferably, with PE, PP and PS together mixed pyrolysis when no longer affect final oily product
Quality.
Mixed waste plastic rubbish of the present invention may include what is isolated after house refuse or rubbish from cooking oversize, compost
Plastics, or the preprocessed plastics isolated of changing food waste and scum silica frost (based on plastics).It is particularly well-suited to house refuse or kitchen
Remaining screen residue of waste, house refuse and rubbish from cooking can produce oversize Jing after mechanical sorting (such as rotary screen, star sieve etc.),
, mainly comprising mixed plastic, rubber, paper, fabric, wood chip etc., mixed plastic is volume parts highest in oversize, is mainly had for it
PE, PP, PS, PET and PVC, volume fraction accounts for more than 70%, is also recovery value highest part.Preferably to make life
Rubbish or rubbish from cooking oversize are applied to the present invention, and the present invention can carry out pre-treatment to the oversize, and it is included on sieve
Thing carries out crushing and screening, to remove the oversize in inorganic matter (such as bone, tile, sandstone etc., can be filled), so
After carry out cleaning removal of impurities, to remove the grease and organic matter of mixed plastic adhesive surface.For the organic matter in the oversize
Part such as stalk, paper and wood chip etc. are that anaerobic methane production project needs to improve the part of recovery ratio, if but being separately separated this portion
Point, economy is poor, but in combination with the present invention, separates organic matter and remove anaerobic methane production, and mixed plastic is for high-efficiency cleaning cracking
Liquefaction, its economy more preferably, additionally due to the organic matter portion of oversize have passed through alkali formula pyrohydrolysis, destroys these organic matters
Surface texture, changes the hydrophobicity on surface, then carries out Anaerobic Treatment, can improve product natural pond rate, reduces the time of staying.In the present invention
The waste water of generation can be used for the cleaning removal of impurities, to reduce the generation of waste water.
On the other hand, the present invention provides a kind of hydro-thermal reaction system for being applied to pyrohydrolysis process in preceding method, described
Hydro-thermal reaction system includes at least two hydrothermal reactors, alkaline solution storage tank, pending mixed waste plastic rubbish storage tank and receipts
Storage, the alkaline solution storage tank is connected respectively by pipeline with every hydrothermal reactor, the pending mixed waste plastic rubbish
Rubbish storage tank is connected respectively by conveying worm with the entrance of every hydrothermal reactor, in the pending mixed waste plastic rubbish
Each exit of storage tank is provided with the baffle plate of control material discrepancy；Coil pipe is provided with every hydrothermal reactor, and every hydro-thermal is anti-
The exit for answering device is provided with coupled heat exchanger, and the outlet of the coil pipe in every hydrothermal reactor (is located at hydrothermal reactor
Lower section) it is connected with the medium inlet of the heat exchanger, the coil inlet (position in every hydrothermal reactor in many hydrothermal reactors
In hydrothermal reactor top) join end to end to each other (such as by taking two hydrothermal reactors as an example, i.e., with the media outlet of the heat exchanger
The media outlet of the heat exchanger being connected with first hydrothermal reactor is connected with the entrance of the coil pipe in second hydrothermal reactor,
The media outlet of the heat exchanger being connected with second hydrothermal reactor is connected with the coil inlet in first hydro-thermal heat exchanger),
The outlet of every hydrothermal reactor is connected after coupled heat exchanger with the collector.Collector is used to collect recovery
Solid phase and water phase after heat.
Hydro-thermal reaction system of the present invention can be applicable to pyrohydrolysis in preceding method and process, and hydro-thermal reaction can be made efficiently to save
The carrying out of energy.
Specific embodiment of the invention, the system includes 2 hydrothermal reactors, respectively the first hydro-thermal
Reactor and the second hydrothermal reactor, the media outlet of the heat exchanger being connected with the first hydrothermal reactor and the second hydrothermal reactor
The entrance of interior coil pipe is connected, in the media outlet of the heat exchanger being connected with the second hydrothermal reactor and the first hydro-thermal heat exchanger
Coil inlet is connected.
Specific embodiment of the invention, the system includes 3 hydrothermal reactors, respectively the first hydro-thermal
Reactor, the second hydrothermal reactor and the 3rd hydrothermal reactor, the media outlet of the heat exchanger being connected with the first hydrothermal reactor
It is connected with the entrance of the coil pipe in the second hydrothermal reactor, the media outlet of the heat exchanger being connected with the second hydrothermal reactor and
Coil inlet in three hydro-thermal heat exchangers is connected, the media outlet and the first hydro-thermal of the heat exchanger being connected with the 3rd hydrothermal reactor
Coil inlet in heat exchanger is connected.
Aforementioned medium can be chosen according to actual conditions, usually conduction oil.The present invention is by arranging at least more than two
Hydrothermal reactor, and coupled together hydrothermal reactor with coil pipe by heat exchanger so that pyrohydrolysis reaction can be energy-efficient
Carrying out.Specifically by taking 3 hydrothermal reactors as an example, when pyrohydrolysis reaction occurs in the first hydrothermal reactor, to second
Mixed waste plastic rubbish and alkaline aqueous solution are input in reactor, after the pyrohydrolysis in first reactor is completed, hot contains
There is TA solution to be injected into coupled heat exchanger by valve, this is produced in quick reduced pressure and part solution containing TA
Water evaporated, most of used heat that the phase transformation of water is greatly improved in thermal transition benefit, solution containing TA passes through phase-change heat-exchange
Gone to heat conduction oil by heat exchanger transfer, the conduction oil is transported to second reactor and carrys out supplementary caloric energy, causes second reactor
In hydrolysis, when hydrolysis process occurs in second reactor, in the 3rd reactor be input into mixed waste plastic rubbish
And alkaline aqueous solution, after the hydro-thermal reaction in second reactor is completed, the solution containing TA of heat is injected into and it by valve
Connected heat exchanger, the used heat containing TA solution is transferred heating conduction oil, and the conduction oil is transported to the 3rd reactor to increase
Concurrent heating amount, with supplementary heat, the hydrolysis of the 3rd reactor is initiated, and carries out in the pyrohydrolysis reaction of the 3rd reactor
During, start the step of being input into mixed waste plastic rubbish and aqueous slkali in first reactor, when in the 3rd reactor
After the completion of pyrohydrolysis reaction, second is followed during the used heat in solution containing TA is transferred to first reactor to supplement first reactor
The heat of the pyrohydrolysis of ring.By this mode that recycles to heat, pyrohydrolysis reaction energy efficiency of the present invention will be than normal
The hydro-thermal process of rule improves at least 15～30%.
Specific embodiment of the invention, the system also includes driving the motor of the conveying worm.
Specific embodiment of the invention, in the system, every hydrothermal reactor is equipped with pressure gauge.
Specific embodiment of the invention, in the system, every hydrothermal reactor is equipped with rupture disk.
In summary, the invention provides using the integrated artistic and hydro-thermal reaction of mixed plastic rubbish high-efficiency cleaning liquefaction
System, is particularly suitable for the efficient utilization of oversize in house refuse or rubbish from cooking integrated treatment, at present most of similar terms
Purpose oversize need to pay burning project, and adopt this technique, not only avoid PET, the PVC in mixed waste plastic to oil product
The adverse effect of matter, energy high-efficiency cleaning liquefaction can also produce high value-added product, such as TA powder or particle, PS regeneration modelings
Material, and simultaneously anaerobic fermentation can also be carried out using the organic matter in screening thing, the economy of this intermediate item is improved, while realizing
More preferable resource circulation utilization.
Description of the drawings
Fig. 1 is the process chart of the embodiment of the present invention 1.
The hydro-thermal reaction system that Fig. 2 is used by the embodiment of the present invention 1, wherein, label has such as meaningful in Fig. 2：
1：#1 baffle plates；2：#1 conveying worms；3：#1 enters valve；4：#1 hydrothermal reactors；5：#1 goes out valve；6：#2 baffle plates；7：#
2 conveying worms；8：#2 enters valve；9：#2 hydrothermal reactors；10：#2 goes out valve；11：#3 baffle plates；12：#3 conveying worms；13：#3
Enter valve；14：#3 hydrothermal reactors；15：#3 goes out valve；16：Conduction oil；17：Coil pipe；18：Pending mixed waste plastic rubbish storage tank；
19：Sodium hydroxide solution storage tank；20：Collector.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, in conjunction with being embodied as
Example carries out described further below to technical scheme, it should be understood that these examples are merely to illustrate the present invention rather than limit
The scope of the present invention processed.In embodiment, each Starting reagents material is commercially available, and the experimental technique of unreceipted actual conditions is
Conventional method known to art and normal condition, or according to the condition proposed by apparatus manufacturer.
Embodiment 1
The present embodiment is provided using the integrated artistic and hydro-thermal reaction system of mixed plastic rubbish high-efficiency cleaning liquefaction, described
The flow process of integrated artistic as shown in figure 1, oversize (the present embodiment oversize is obtained Jing after broken bag for rubbish from cooking by rotary screen
, main component is plastics (containing PP, PE, PS, PET and PVC), paper, bamboo and wood, also including bone, tile and is attached to
Sandstone above material, wherein mixed plastic partial volume fraction is more than 70%.) by crushing and screening, remove bone, tile and
The raw materials such as the inorganic matters such as sandstone, acquirement waste plastics, waste paper, bamboo and wood；Next step cleaning removal of impurities is carried out, the oil of adhesive surface is removed
Fat and other organic matters；PET is converted into the product such as terephthalic acid (TPA) (TA) and ethylene glycol (EG) by next step by pyrohydrolysis
(water phase), the chlorine in PVC is converted, and into water phase, produces not chloride intermediate product, and keep the plastics such as PE/PP//PS (Gu
Phase) quality it is unaffected, water phase (containing clarified solution and suspension) and solid phase (mainly PP, PE and PS) are then peeled off, by institute
Obtaining solid phase carries out thermal cracking liquefaction, and after water is mutually layered, the aqueous portion (being rich in TA and EG) of clarification enters TA productions and separates and fills
Put, to produce TA powder/granules, the waste water containing EG returns to cleaning impurity removing equipment and utilizes；Muddy (suspension) aqueous portion
Through filtration and cake dewatering, organic matter fractions (filter cake part) are separated the waste water for anaerobic methane production, separated
Cleaning is returned to except hetero moiety is recycled；When the index such as COD is too high in waste water, into after sewerage process, recycle
In purging system.
Fig. 2 is the hydro-thermal reaction system for being applied to the present embodiment method, and the system includes 3 hydrothermal reactors, i.e. #1
Hydrothermal reactor 4 (the first hydrothermal reactor), #2 hydrothermal reactors 9 (the second hydrothermal reactor), #3 hydrothermal reactors 14 the (the 3rd
Hydrothermal reactor), sodium hydroxide solution storage tank 19 (alkaline solution storage tank), pending mixed waste plastic rubbish storage tank 18 and collect
Device 20, the sodium hydroxide solution storage tank 19 by pipeline and #1 enter valve 3, #2 enter valve 8 and #3 to enter valve 13 anti-with #1 hydro-thermals respectively
Device 4, #2 hydrothermal reactors 9 and #3 hydrothermal reactors 14 is answered to connect, pending mixed waste plastic rubbish storage tank 18 passes through respectively #1
Conveying worm 2, #2 conveying worms 7 and #3 conveying worms 12 respectively with #1 hydrothermal reactors 4, #2 hydrothermal reactors 9 and #
The entrance of 3 hydrothermal reactors 14 is connected, and is respectively equipped with each exit of the pending mixed waste plastic rubbish storage tank 18
#1 baffle plates 1, #2 baffle plates 6 and #3 baffle plates 11 that control material comes in and goes out；Coil pipe 17, and 3 are respectively provided with 3 hydrothermal reactors
The exit of hydrothermal reactor to be respectively equipped with go out valve 5, #2 by #1 and go out valve 10, #3 and goes out the coupled heat exchanger of valve 15, per only
Medium (conduction oil 16) entrance phase of the outlet (being located at hydrothermal reactor lower section) of the coil pipe in hydrothermal reactor with the heat exchanger
Even, in every hydrothermal reactor coil inlet (being located at hydrothermal reactor top) is first to each other with the media outlet of the heat exchanger
Tail is connected, i.e., the entrance phase of the media outlet of the heat exchanger being connected with #1 hydrothermal reactors 4 and the coil pipe of #2 hydrothermal reactors 9
Even, the media outlet of the heat exchanger being connected with #2 hydrothermal reactors 9 is connected with the coil inlet of #3 hydrothermal reactors 14, with #3 water
The media outlet of the connected heat exchanger of thermal reactor 14 is connected with the coil inlet of #1 hydrothermal reactors 4, every hydrothermal reactor
Outlet be connected with the collector 20 after coupled heat exchanger, #1 conveying worms 2, #2 conveying worms 7 and #
3 conveying worms 12 share a motor, and on 3 hydrothermal reactors pressure gauge and rupture disk are equipped with.Collector 20 is used to receive
Collection reclaims solid phase and water phase after heat.
Aforementioned hydro-thermal reaction system is run as follows, opens #1 baffle plates 1, and by after crushing and screening and cleaning removal of impurities
Mixed waste plastic rubbish be added in pending mixed waste plastic rubbish storage tank 18, Motor drive #1 conveying worm 2 will be treated
Process mixed waste plastic rubbish to be transported in #1 hydrothermal reactors 4 from storage tank, now, two other #2 baffle plates 6 and #3 baffle plates
11 remain off；When the mixed waste plastic rubbish of supply reaches 5Kg, #1 baffle plates 1 are closed；In sodium hydroxide solution storage tank 19
NaOH solution be added in #1 hydrothermal reactors 4 by #1 valves 3, the concentration of the NaOH solution is 0.3mol/L；Add
Volume is 20L；Then, the reactor is pressurized to 22bar and is heated to 200 DEG C of initiation hydrolysis, and continue 2 altogether～
3 hours, in the hydro-thermal reaction step, PET was converted to high-purity TA, did not had the harmful side product come from other plastics etc..
By the hydro-thermal reaction, TA can reach up to 98% conversion ratio.When hydrolysis occurs in #1 hydrothermal reactors 4,
The mixed waste plastic rubbish of mixing is input into in #2 hydrothermal reactors 9, #2 baffle plates 6 are opened, #1 baffle plates 1 and #3 baffle plates 11 is closed.
The motor of three conveying worms is driven from driving #1 conveying worms 2 to be switched to driving #2 conveying worms 7, by what is mixed
Mixed waste plastic rubbish is transported to #2 hydrothermal reactors 9, and in the mixed waste plastic rubbish of the mixing of input 5Kg is reached, and closes #2
Baffle plate 6, the NaOH solution in sodium hydroxide solution storage tank 19 is added in #2 hydrothermal reactors 9 by #2 valves 8, and its volume is
20L.After hydrolysis in #1 hydrothermal reactors 4 is completed, the solution containing TA of heat is injected into heat exchanger by #1 valves 5, this generation
Quickly the water in reduced pressure and part solution containing TA is evaporated, and the phase transformation of water greatly improves thermal transition benefit, contains
Most of used heat in TA solution is transferred heating conduction oil by phase-change heat-exchange, and the conduction oil is transported to #2 hydro-thermal reactions
Device 9 carrys out supplementary caloric energy, and with supplementary heat, the hydrolysis of #2 hydrothermal reactors 9 is initiated, and by #1 hydro-thermal reactions
Identical condition is carried out in device 4.When hydrolysis occurs in #2 hydrothermal reactors 9, it is input into in #3 hydrothermal reactors 14
The mixed waste plastic rubbish of mixing, opens #3 baffle plates 11, closes #1 baffle plates 1 and #2 baffle plates 6, and motor is from driving #2 conveying worms
7 are switched to driving #3 conveying worms 12, and the mixed waste plastic rubbish of mixing is transported in #3 hydrothermal reactors 14.Defeated
The mixed plastic rubbish for entering reaches 5Kg, closes #3 baffle plates 11, and the 20L NaOH solutions in sodium hydroxide solution storage tank 19 pass through #3
Valve 13 is added in #3 hydrothermal reactors 14, and after the hydrolysis in #2 hydrothermal reactors 9 is completed, the solution containing TA of heat leads to
Cross #2 valves 10 and be injected into heat exchanger.The used heat of TA solution is transferred heating conduction oil 16, and the conduction oil is transported to #3 water
With additional heat, with supplementary heat, the hydrolysis of #3 hydrothermal reactors 14 is initiated coil pipe in thermal reactor 14, and
And by carrying out with identical condition in #1 reactors 4.During the hydrolysis of #3 hydrothermal reactors 14 is carried out, start
The step of as previously described the mixed waste plastic rubbish and NaOH solution of mixing being input into in #1 hydrothermal reactors 4, when #3 hydro-thermals
After the completion of hydrolysis in reactor 14, it is anti-to supplement #1 hydro-thermals that the used heat in TA solution is transferred to #1 hydrothermal reactors 4
Answer the heat of the hydrolysis of second circulation in device 4.In subsequent hydro-thermal reaction, partial heat is from generation in previous reactor
Previous hydro-thermal reaction in reclaim.In this way, designed energy efficiency will be improved at least than conventional hydro-thermal process
15～30%.
Material after hydro-thermal process by separate solid phase and water phase (mixed plastic, water phase standing separation obtains fining end
Divide (rich in TA), muddy part (suspension, rich in organic matter).Clarified solution can mix to reclaim TA rich in TA with inorganic acid；
After filtering, filter cake can be used for anaerobic methane production to suspension, make full use of organic matter treatment facility in factory (for example to add organic matter
Enter the anaerobic methane production system of rubbish from cooking/changing food waste, increase biogas output), the wastewater fraction of generation can be used for cleaning and remove
Miscellaneous, the needing of the high COD in part enters sewage disposal system；Solid product is the desirable feedstock for cracking liquefaction, for producing
Bunker oil more than CST180 standards, if scale is annual more than 50,000 tons, can increase fractionating column, and production added value is higher
Gasoline, light diesel fuel and bunker oil.
The schematic diagram only show the combination of 3 reactors, but the method is applied to 2 reactors for only reaching the above, this
Depending on the needs of user.
Mixed plastic after drying, the continuous of isolation air is sent into by double-spiral feeder by the mixed plastic isolated
Formula heat scission reaction kettle, at 420 DEG C, under molecular sieve catalyst Y-zeolite catalysis, the Jing reactions of 30 minutes are converted into
The cracked oil of high-quality, reaches quality more than CST180 bunker oil standards, shown in table specific as follows 1：
Table 1
Comparative example 1
Embodiment 1 is directly cleaned the mixed waste plastic rubbish mixed after removal of impurities carries out as described in Example 1 cracking system
Oil reaction, the product of the direct thermal cracking of mixed plastic, its overall mechanical impurity content height be unsatisfactory for CST180 standards requirement, need by
The pale yellow powder that PET thermal crackings are produced is filtered out, and the solid residue that this Partial filtration goes out (with organic acid as main component)
There is intense irritation smell to be difficult by.PET produces a large amount of solid phase organic acids under above cracking conditions；PVC thermal cracking meetings
Produce byproduct hydrogen chloride.Organic acid and hydrogen chloride product that more importantly PET and PVC thermal crackings are produced, will be to catalyst
Life-span adversely affect, and have corrosiveness to cracking apparatus, byproduct hydrogen chloride and the water in material of particularly PVC cracking
Divide plus thermogenetic vapor is combined, have severe corrosive to equipment.Organic acid and hydrogen chloride are remained in oily product also can be affected
The quality of oil, stability and its utilization.
Comparative example 1 is it can be seen that by the present invention, first, the mixed plastic and organic matter in oversize is obtained most
The recycling of big degree, and its product TA, bunker oil quality and biogas quality better, added value is high；Second, for sieve
Mixed plastic part in upper thing, compound pyrohydrolysis+cracking oil-producing technique efficiently avoid PET and PVC pyrolysis products pair and set
Having a strong impact on for standby and catalyst, increased TA products, and cause oil product up to standard and more stable.
What is finally illustrated is：Above example is merely to illustrate the implementation process and feature of the present invention, and unrestricted is sent out
Bright technical scheme, although being described in detail to the present invention with reference to above-described embodiment, one of ordinary skill in the art should
Work as understanding：Still the present invention can be modified or equivalent, without departing from the spirit and scope of the present invention any
Modification or local are replaced, and all should be covered in the middle of protection scope of the present invention.
Claims (10)
1. a kind of method of utilization mixed waste plastic junk-free liquefaction, methods described comprises the steps：
(1) under conditions of temperature is 160～300 DEG C and pressure is 20～220bar, using alkaline aqueous solution to the useless modeling of mixing
Material rubbish carries out pyrohydrolysis process；
The mixed waste plastic rubbish contains one or more in PE, PP, PS, and PET, the selective mixed waste plastic rubbish
May also include PVC；
It is preferred that the mixed waste plastic rubbish contains PE, PP, PS, PET and PVC；
(2) the water phase in the material after hydro-thermal process is separated with solid phase, isolated solid phase is carried out into liquefaction.
2. method according to claim 1, wherein, the alkaline aqueous solution is selected from Ca (OH)2The aqueous solution, Ba (OH)2It is water-soluble
One or more in liquid, the KOH aqueous solution, the NaOH aqueous solution and the CsOH aqueous solution, the preferred NaOH aqueous solution, further preferably
Ground, the concentration of the alkaline aqueous solution is 0.3mol/L～1.7mol/L；
Preferably, the alkaline aqueous solution and the volume mass ratio of the mixed waste plastic rubbish are 2～5L:1Kg.
3. method according to claim 1, wherein, the liquefaction is cracking liquefaction；Preferably, it comprises the steps：
The isolated solid phase of step (2) is sent into into the heat scission reaction kettle of isolation air, at 380～460 DEG C, in molecular sieve
It is reacted to be converted into cracked oil under catalyst.
4. method according to claim 1, wherein, when containing PS, and PE and/or PP in the mixed waste plastic rubbish
When, the PS and PE in step (2) gained solid phase and/or PP point are opened using density-sorting methods, using PE and/or PP liquefactions, make
Granulated with PS.
5. the method according to any one of Claims 1 to 4, wherein, with water phase isolated in step (2) in it is clear
Clear part prepares terephthalic acid powder or particle for raw material, reclaims the waste water profit capable of circulation containing ethylene glycol after terephthalic acid (TPA)
With, then enter back into anaerobic system produce natural pond.
6. the method according to any one of Claims 1 to 4, wherein, will be muddy in water phase isolated in step (2)
Filter cake part is used for anaerobic methane production, the waste water reusable edible separated by turbid part through filtration and cake dewatering.
7. the method according to any one of Claims 1 to 4, wherein, the mixed waste plastic rubbish includes house refuse
Or the plastics isolated after rubbish from cooking oversize, compost or the preprocessed plastics isolated of changing food waste and scum silica frost；It is preferred that
Ground, the mixed waste plastic rubbish is house refuse or rubbish from cooking oversize；
When the mixed waste plastic rubbish is house refuse or rubbish from cooking oversize, methods described includes entering the oversize
Row pre-treatment, the pre-treatment includes carrying out crushing and screening to oversize, to remove the oversize in inorganic matter, Ran Houjin
Row cleaning removal of impurities, to remove the grease and organic matter of mixed plastic adhesive surface.
8. a kind of hydro-thermal reaction system for being applied in method any one of claim 1～7 carry out pyrohydrolysis process, institute
System is stated including at least two hydrothermal reactors, alkaline solution storage tank, pending mixed waste plastic rubbish storage tank and collectors, institute
State alkaline solution storage tank to be connected with every hydrothermal reactor respectively by pipeline, the pending mixed waste plastic rubbish storage tank point
Not Tong Guo conveying worm be connected with the entrance of every hydrothermal reactor, in the every of the pending mixed waste plastic rubbish storage tank
Individual exit is provided with the baffle plate of control material discrepancy；It is provided with coil pipe in every hydrothermal reactor, and every hydrothermal reactor goes out
Coupled heat exchanger, the outlet of the coil pipe in every hydrothermal reactor and the medium inlet phase of the heat exchanger are provided with mouthful
Connect, the media outlet of the coil inlet in every hydrothermal reactor in many hydrothermal reactors and the heat exchanger is to each other from beginning to end
It is connected, the outlet of every hydrothermal reactor is connected after coupled heat exchanger with the collector.
9. hydro-thermal reaction system according to claim 8, wherein, the system includes 3 hydrothermal reactors, respectively
For the first hydrothermal reactor, the second hydrothermal reactor and the 3rd hydrothermal reactor, the heat exchanger being connected with the first hydrothermal reactor
Media outlet be connected with the entrance of the coil pipe of the second hydrothermal reactor, the medium of the heat exchanger being connected with the second hydrothermal reactor
Outlet is connected with the coil inlet of the 3rd hydro-thermal heat exchanger, the media outlet of the heat exchanger being connected with the 3rd hydrothermal reactor and the
The coil inlet of one hydro-thermal heat exchanger is connected.
10. hydro-thermal reaction system according to claim 8, wherein, the system also includes driving the conveying worm
Motor.
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