CN106635115B - Utilize the method and hydro-thermal reaction system of mixed waste plastic rubbish high-efficiency cleaning liquefaction - Google Patents
Utilize the method and hydro-thermal reaction system of mixed waste plastic rubbish high-efficiency cleaning liquefaction Download PDFInfo
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- CN106635115B CN106635115B CN201611176700.1A CN201611176700A CN106635115B CN 106635115 B CN106635115 B CN 106635115B CN 201611176700 A CN201611176700 A CN 201611176700A CN 106635115 B CN106635115 B CN 106635115B
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- 239000004033 plastic Substances 0.000 title claims abstract description 106
- 229920003023 plastic Polymers 0.000 title claims abstract description 106
- 239000010813 municipal solid waste Substances 0.000 title claims abstract description 77
- 239000010812 mixed waste Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004140 cleaning Methods 0.000 title claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012071 phase Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000007790 solid phase Substances 0.000 claims abstract description 18
- 239000005416 organic matter Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000012216 screening Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005336 cracking Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- 238000010411 cooking Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000010504 bond cleavage reaction Methods 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002361 compost Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000855 fermentation Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 238000003860 storage Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 230000007062 hydrolysis Effects 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 239000002699 waste material Substances 0.000 description 13
- 238000004064 recycling Methods 0.000 description 7
- 238000004227 thermal cracking Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000002918 waste heat Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000010512 thermal transition Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010759 marine diesel oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention provides the method and hydro-thermal reaction system using mixed waste plastic rubbish high-efficiency cleaning liquefaction, the method includes under conditions of temperature is 160~300 DEG C and pressure is 20~220bar, pyrohydrolysis processing is carried out to mixed waste plastic rubbish using alkaline aqueous solution；The mixed waste plastic rubbish may also include PVC containing one or more of PE, PP, PS and PET, the selective mixed waste plastic rubbish；Water phase in material after hydro-thermal process is detached with solid phase, isolated solid phase is subjected to liquefaction.Invention not only avoids PET, PVC in mixed waste plastic to the adverse effect of oil quality, energy high-efficiency cleaning liquefaction, high value-added product can also be generated, such as TA powder or particle, PS regenerated plastics, and can also anaerobic fermentation be carried out using the organic matter in screening object simultaneously, improve the economy of this intermediate item, while realizing better resource circulation utilization.
Description
Technical field
The method and hydro-thermal reaction system that the present invention relates to the use of mixed plastic rubbish high-efficiency cleaning liquefaction belong to rubbish and return
Receive process field.
Background technology
It is a long-term technical issues that need to address that the resource utilization of rubbish, which utilizes, while being also one and being concerned
Social concern.Waste plastics is an important component of rubbish, and Volume of Waste Plastics is fluffy, it is big to occupy volume, according to measuring and calculating,
The loose bulk density of waste plastics is 55~66kg/m in house refuse3.Rubbish containing waste plastics accounted for when landfill stabilization
With storage capacity, and because degradation speed is slow, seriously affect Landfill Stabilization Rate process；And when being burned, easily generate dioxin etc.
Severe pollutant.The prior art exists to the waste plastics in rubbish by sorting enrichment to improve the content of plastics, then to it
It carries out thermal cracking and produces method of the oil to realize waste plastics recycling.However, although 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.To find out its cause, mainly from rubbish
The waste plastics of recycling in rubbish is mixing, and composition is complicated, often the mixture of a variety of plastics, usually PE, PP, PS, PET
With the mixture of PVC, between these plastics and waste plastics and the rubber, paper, fabric, the sawdust that wherein mix etc. are to mixed plastic
Crack characteristic, product distribution have extremely complex influence.
As described above, such as mixed plastic PE, PP, PS, PET and PVC mixed plastic recycled from rubbish is directly carried out
Liquefaction is cracked, then the fuel oil low quality generated produces 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 aoxidized, property is unstable, and PE, PP and the pyrolysis product of PS plastic ratio
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 points are opened, extremely difficult, mainly due to being often attached to the impurity such as grease, dirt and swill on mixed plastic,
So that common wet method density separation and electrostatic separation inefficiency, the classification rate of recovery of various plastics are low.Such as use a large amount of water
Cleaning is sorted again after dry, and it will cause very high water consume and energy consumptions, and mixing of branching away speckles with dirt
The PET and PVC of dirt are difficult to recycle.
In summary, there is an urgent need for develop a kind of method and system using mixed waste plastic rubbish high-efficiency cleaning liquefaction for this field
To carry out high efficiente callback utilization to mixed waste plastic.
Invention content
The main purpose of the present invention is to provide a kind of method using mixed waste plastic junk-free liquefaction, this method energy
Enough make the fuel oil quality that mixed plastic is prepared high, while can efficiently generate high value added product, while the three wastes generate less.
System that pyrohydrolysis handles that it is still another object of the present invention to provide a kind of suitable for the above method.It is using this
System can be energy-efficient carry out the method.
To achieve the above object, the present invention provides a kind of method using mixed waste plastic junk-free liquefaction, the side
Method includes the following steps：
(1) it is 160~300 DEG C in temperature and pressure is 20~220bar (such as 30bar, 50bar, 100bar, 200bar
Deng) under conditions of, pyrohydrolysis processing is carried out to mixed waste plastic rubbish using alkaline aqueous solution；
The mixed waste plastic rubbish is containing one or more of 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) water phase in the material after hydro-thermal process is detached with solid phase, isolated solid phase is subjected to liquefaction.
The invention is handled mixed waste plastic rubbish using pyrohydrolysis reaction, by mixed waste plastic rubbish
PET in rubbish is converted into the products such as terephthalic acid (TPA) (TA) and ethylene glycol (EG) and enters water phase, and keeps PE, PP, and/or PS
The quality of equal plastics solid phase is unaffected, and when as contained PVC in mixed waste plastic rubbish, pyrohydrolysis reaction turns the chlorine in PVC
Change, into water phase, generate the intermediate product without chlorine, which also can go to make together with the plastics such as PE, PP, and/or PS
Oil avoids the influence of PET and/or PVC to liquefaction in mixed waste plastic rubbish.
Specific implementation method according to the present invention, in the method for the invention, the alkaline aqueous solution is selected from Ca (OH)2
Aqueous solution, Ba (OH)2It is one or more in aqueous solution, KOH aqueous solutions, NaOH aqueous solutions and CsOH aqueous solutions, preferably NaOH
Aqueous solution, it is further preferred that a concentration of 0.3mol/L~1.7mol/L of the alkaline aqueous solution.
Specific implementation mode according to the present invention, in the method for the invention, the alkaline aqueous solution is mixed with described
The volume mass ratio of waste plastic garbage is 2~5L:1Kg.
Liquefaction of the present invention can refer to prior art progress, it is preferable that the liquefaction is cracking oil-producing, more preferably
Ground comprising following steps：
The heat scission reaction kettle that solid phase (mixed plastic) obtained by step (2) is sent 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 mould
Expect the ratio of 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 reaction in 10min~1h hours, this depends on reactor types).Experiment shows the high-quality converted by the present invention
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 implementation mode according to the present invention contains in the method for the invention when in the mixed waste plastic rubbish
When having PS and PE and/or PP, using density-sorting methods by solid phase obtained by step (2) PS and PE and/or PP points open, use
PE and/or PP liquefactions, are granulated using PS.Since all types of plastic density is different, part (such as the PE/PP of water can will be lighter than
Equal mixed plastics) it is detached with the part (such as PS) for overweighting water, make the regenerated plastics particle of PS production higher qualities, it is useless to realize
The resource utilization of plastic garbage utilizes.The density-sorting methods can refer to prior art progress.
Specific implementation mode according to the present 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, the waste water containing ethylene glycol can follow after recycling terephthalic acid (TPA)
Ring utilizes (such as cleaning equipment or cleaning removal of impurities), then enters back into anaerobic system production natural pond.As previously mentioned, step of the present invention
PET is recycled well, the water phase clarified solution after decomposition can produce high-purity TA powder or particle.
Specific implementation mode according to the present invention, in the method for the invention, by water phase isolated in step (2)
In muddy part by filtering and cake dewatering, by filter cake part (mainly organic matter, including stalk, sawdust, paper etc.) point
It is Ke Xunhuanliyong (such as cleaning equipment or cleaning removal of impurities) to separate out the waste water separated to be used for anaerobic methane production.When in waste water
When the indexs such as COD are excessively high, into after sewerage processing, it is recycling in cleaning system.
After water phase is detached with solid phase in the present invention, stratification, upper part is clarification part, and lower part is muddy part.
The present invention can recycle PET very well, and can produce high-purity TA powder or particle, PS regenerated plastics particles etc.
High value added product, at the same time, when containing PVC, PVC will be converted simultaneously, wherein cleavage reaction occurs, contained by PVC
Chlorine element converts, and almost all enters water phase so that when solid product is used for liquefaction after conversion, when such as thermal cracking oil-producing, almost
Hydrogen chloride is no longer generated, and the quality of oil product is preferable, no longer influences final oily product when mixed pyrolysis together with PE, PP and PS
Quality.
What mixed waste plastic rubbish of the present invention may include isolating after house refuse or rubbish from cooking oversize, compost
Plastics or the preprocessed plastics isolated of kitchen garbage and dross (based on plastics).Especially suitable for house refuse or kitchen
Remaining screen residue of waste, house refuse and rubbish from cooking will produce oversize after mechanical sorting (such as rotary screen, star sieve etc.),
It includes mainly mixed plastic, rubber, paper, fabric, sawdust etc., and mixed plastic is volume parts highest in oversize, is mainly had
PE, PP, PS, PET and PVC, volume fraction account for 70% or more and the highest part of recovery value.Preferably to make life
Rubbish or rubbish from cooking oversize are suitable for the present invention, and the present invention can carry out pre-treatment to the oversize comprising on sieve
Object carries out crushing and screening, to remove the inorganic matter in the oversize (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 is that anaerobic methane production project needs to improve the part of recycling ratio such as stalk, paper and sawdust, if but being separately separated this portion
Point, economy is poor, but is combined with the present invention, and separation organic matter goes anaerobic methane production, mixed plastic to be cracked for high-efficiency cleaning
Liquefaction, economy is more preferable, 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, and production natural pond rate can be improved, reduce the residence time.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 handled applied to pyrohydrolysis 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 are connect with every hydrothermal reactor respectively by pipeline, the pending mixed waste plastic rubbish
Rubbish storage tank is connected by screw conveyor with the entrance of every hydrothermal reactor respectively, in the pending mixed waste plastic rubbish
Each exit of storage tank is equipped with the baffle that control material comes in and goes out；Coil pipe is equipped in every hydrothermal reactor, and every hydro-thermal is anti-
The exit of device is answered to be equipped with coupled heat exchanger, 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 more hydrothermal reactors
Above hydrothermal reactor) it joins 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 for 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 for 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 after coupled heat exchanger with the collector by being connected.Collector is recycled for collecting
Solid phase after heat and water phase.
Hydro-thermal reaction system of the present invention can be applied to pyrohydrolysis in preceding method and handle, and hydro-thermal reaction can be made efficiently to save
The progress of energy.
Specific implementation mode according to the present invention, the system comprises 2 hydrothermal reactors, respectively the first hydro-thermal
Reactor and the second hydrothermal reactor, the media outlet for 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 for the heat exchanger being connected with the second hydrothermal reactor and the first hydro-thermal heat exchanger
Coil inlet is connected.
Specific implementation mode according to the present invention, the system comprises 3 hydrothermal reactors, respectively the first hydro-thermal
Reactor, the second hydrothermal reactor and third hydrothermal reactor, the media outlet for 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 for the heat exchanger being connected with the second hydrothermal reactor and
Coil inlet in three hydro-thermal heat exchangers is connected, the media outlet for the heat exchanger being connected with third hydrothermal reactor and the first hydro-thermal
Coil inlet in heat exchanger is connected.
Aforementioned medium can be chosen according to actual conditions, usually conduction oil.The present invention is by being arranged at least two or more
Hydrothermal reactor, and connected hydrothermal reactor with coil pipe by heat exchanger so that pyrohydrolysis reaction can be energy-efficient
Progress.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 inputted in reactor, after the pyrohydrolysis in first reactor is completed, hot contains
There is TA solution to be injected coupled heat exchanger by valve, this is generated in quick pressure reduction and part solution containing TA
Water be evaporated, the phase transformation of water greatly improves thermal transition benefit, and most of waste heat in solution containing TA passes through phase-change heat-exchange
It goes heating conduction oil, the conduction oil to be transported to second reactor and carry out supplementary caloric energy by heat exchanger transfer, causes second reactor
In hydrolysis, when hydrolysis process occurs in the second reactor, into third reactor input mixed waste plastic rubbish
And alkaline aqueous solution, after the hydro-thermal reaction in second reactor is completed, hot solution containing TA is injected by valve and it
The waste heat of connected heat exchanger, the solution containing TA is transferred heating conduction oil, which is transported to third reactor to increase
Concurrent heating amount, with the heat of supplement, the hydrolysis of third reactor is initiated, and is reacted and is carried out in the pyrohydrolysis of third reactor
During, start the step of mixed waste plastic rubbish and aqueous slkali are inputted into first reactor, when in third reactor
After the completion of pyrohydrolysis reaction, the waste heat in solution containing TA is transferred to first reactor and is followed with supplementing in first reactor second
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 implementation mode according to the present invention, the system also includes the motors for driving the screw conveyor.
Specific implementation mode according to the present invention, in the system, every hydrothermal reactor are equipped with pressure gauge.
Specific implementation mode according to the present invention, in the system, every hydrothermal reactor are equipped with rupture disk.
In summary, the present invention provides the integrated artistics and hydro-thermal reaction using mixed plastic rubbish high-efficiency cleaning liquefaction
System, particularly suitable for the efficient utilization of oversize in house refuse or rubbish from cooking integrated treatment, current most of similar terms
Purpose oversize need to pay burning project, and use this technique, not only avoid PET, PVC in mixed waste plastic to oil product
The adverse effect of matter, energy high-efficiency cleaning liquefaction can also generate high value-added product, such as TA powder or particle, PS regeneration modelings
Material, and can also anaerobic fermentation be carried out using the organic matter in screening object simultaneously, the economy of this intermediate item is improved, is realized simultaneously
Better resource circulation utilization.
Description of the drawings
Fig. 1 is the process flow chart of the embodiment of the present invention 1.
Fig. 2 is hydro-thermal reaction system used in the embodiment of the present invention 1, wherein label has as significant in Fig. 2：
1：#1 baffles；2：#1 screw conveyors；3：#1 is into valve；4：#1 hydrothermal reactors；5：#1 goes out valve；6：#2 baffles；7：#
2 screw conveyors；8：#2 is into valve；9：#2 hydrothermal reactors；10：#2 goes out valve；11：#3 baffles；12：#3 screw conveyors；13：#3
Into 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 implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, in conjunction with specific implementation
Example carries out technical scheme of the present invention described further below, 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 test method without specific conditions is
Conventional method and normal condition known to fields, or according to the condition proposed by apparatus manufacturer.
Embodiment 1
It is described the present embodiment provides the integrated artistic and hydro-thermal reaction system using mixed plastic rubbish high-efficiency cleaning liquefaction
The flow of integrated artistic as shown in Figure 1, oversize (the present embodiment oversize is that rubbish from cooking is obtained after broken bag by rotary screen
, main component is plastics (containing PP, PE, PS, PET and PVC), paper, bamboo and wood, further includes bone, tile and is attached to
Sandstone above material, wherein mixed plastic partial volume score are more than 70%.) by crushing and screening, removal bone, tile and
The inorganic matters such as sandstone, the raw materials such as acquirement waste plastics, waste paper, bamboo and wood；Cleaning removal of impurities in next step is carried out, the oil of adhesive surface is removed
Fat and other organic matters；In next step by pyrohydrolysis, it converts PET to the products such as terephthalic acid (TPA) (TA) and ethylene glycol (EG)
(water phase) converts the chlorine in PVC, into water phase, generates the intermediate product without chlorine, 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 (being mainly PP, PE and PS) are then detached, by institute
It obtains solid phase and carries out thermal cracking liquefaction, after water phase layering, clear aqueous portion (being rich in TA and EG) enters TA productions and detaches dress
It sets, to produce TA powder/granules, the waste water containing EG returns to cleaning impurity removing equipment and utilizes；Muddy (suspension) aqueous portion
By filtering and cake dewatering, organic matter fractions (filter cake part) are separated into the waste water for anaerobic methane production, separated
Cleaning is returned to except hetero moiety recycles；When the indexs such as COD are excessively high in waste water, into after sewerage processing, recycle
In cleaning system.
Fig. 2 is the hydro-thermal reaction system applied to the present embodiment method, and the system comprises 3 hydrothermal reactors, i.e. #1
Hydrothermal reactor 4 (the first hydrothermal reactor), #2 hydrothermal reactors 9 (the second hydrothermal reactor), 14 (third of #3 hydrothermal reactors
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 are anti-with #1 hydro-thermals respectively into valve 8 and #3 into valve 13 into valve 3, #2 by pipeline and #1
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 #1 respectively
Screw conveyor 2, #2 screw conveyors 7 and #3 screw conveyors 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 in each exit of the pending mixed waste plastic rubbish storage tank 18
#1 baffles 1, #2 baffles 6 and the #3 baffles 11 that control material comes in and goes out；Coil pipe 17, and 3 are respectively equipped in 3 hydrothermal reactors
The exit of hydrothermal reactor be respectively equipped with valve 5 is gone out by #1, #2 goes out valve 10, #3 goes out the coupled heat exchanger of valve 15, every
Medium (conduction oil 16) the entrance phase of the outlet (being located at below hydrothermal reactor) of coil pipe in hydrothermal reactor with the heat exchanger
Even, the coil inlet in every hydrothermal reactor (being located above hydrothermal reactor) 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 for the heat exchanger being connected with #1 hydrothermal reactors 4 and the coil pipe of #2 hydrothermal reactors 9
Even, the media outlet for 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 by being connected with the collector 20 after coupled heat exchanger, #1 screw conveyors 2, #2 screw conveyors 7 and #
3 screw conveyors 12 share a motor, and pressure gauge and rupture disk are equipped on 3 hydrothermal reactors.Collector 20 is for receiving
Solid phase and water phase after collection recycling heat.
Aforementioned hydro-thermal reaction system is run as follows, opens #1 baffles 1, and will be 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 driving #1 screw conveyors 2 will wait for
Processing mixed waste plastic rubbish is transported to from storage tank in #1 hydrothermal reactors 4, at this point, two other #2 baffles 6 and #3 baffles
11 remain off；When the mixed waste plastic rubbish of supply reaches 5Kg, closing #1 baffles 1；In sodium hydroxide solution storage tank 19
NaOH solution be added in #1 hydrothermal reactors 4 by #1 valves 3, a concentration of 0.3mol/L of the NaOH solution；It is added
Volume is 20L；Then, which is pressurized to 22bar and is heated to 200 DEG C of initiation hydrolysis, and continue 2 in total~
3 hours, in the hydro-thermal reaction step, PET was converted to high-purity TA, the harmful side product not 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 that mixing is inputted into #2 hydrothermal reactors 9, opens #2 baffles 6, closes #1 baffles 1 and #3 baffles 11.
The motor of three screw conveyors is driven to be switched to driving #2 screw conveyors 7 from driving #1 screw conveyors 2, by mixing
Mixed waste plastic rubbish is transported to #2 hydrothermal reactors 9, reaches 5Kg in the mixed waste plastic rubbish of the mixing of input, closes #2
Baffle 6, the NaOH solution in sodium hydroxide solution storage tank 19 are added to by #2 valves 8 in #2 hydrothermal reactors 9, and volume is
20L.After hydrolysis in #1 hydrothermal reactors 4 is completed, hot solution containing TA is by #1 valves 5 by injection heat exchanger, this generation
Water in quick pressure reduction and part solution containing TA is evaporated, and the phase transformation of water greatly improves thermal transition benefit, contains
Most of waste heat in TA solution is transferred heating conduction oil by phase-change heat-exchange, which is transported to #2 hydro-thermal reactions
Device 9 carrys out supplementary caloric energy, and with the heat of supplement, the hydrolysis of #2 hydrothermal reactors 9 is initiated, and by #1 hydro-thermal reactions
Identical condition carries out in device 4.When hydrolysis occurs in #2 hydrothermal reactors 9, inputted into #3 hydrothermal reactors 14
The mixed waste plastic rubbish of mixing opens #3 baffles 11, closes #1 baffles 1 and #2 baffles 6, and motor is from driving #2 screw conveyors
7 are switched to driving #3 screw conveyors 12, and the mixed waste plastic rubbish of mixing is transported in #3 hydrothermal reactors 14.Defeated
The mixed plastic rubbish entered reaches 5Kg, closes #3 baffles 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, hot solution containing TA is logical
#2 valves 10 are crossed by injection heat exchanger.The waste heat of TA solution is transferred heating conduction oil 16, which is transported to #3 water
Coil pipe in thermal reactor 14 is with additional heat, and with the heat of supplement, the hydrolysis of #3 hydrothermal reactors 14 is initiated, and
And it is carried out by the identical condition with #1 reactors 4.During the hydrolysis of #3 hydrothermal reactors 14 carries out, start
The step of mixed waste plastic rubbish and NaOH solution of mixing are inputted into #1 hydrothermal reactors 4 as previously described, when #3 hydro-thermals
After the completion of hydrolysis in reactor 14, it is anti-to supplement #1 hydro-thermals that the waste heat in TA solution is transferred to #1 hydrothermal reactors 4
Answer the heat of the hydrolysis of second cycle in device 4.In subsequent hydro-thermal reaction, partial heat is from being happened at previous reactor
Previous hydro-thermal reaction in recycle.In this way, designed energy efficiency will improve at least than conventional hydro-thermal process
15~30%.
Material after hydro-thermal process by detach solid phase and water phase (mixed plastic, water phase standing separation obtain fining end
Divide and (be rich in TA), muddy part (suspension is rich in organic matter).Clarified solution can be mixed with inorganic acid to recycle TA rich in TA；
After filtering, filter cake can be used for anaerobic methane production to suspension, and organic matter treatment facility in factory is made full use of (such as to add organic matter
Enter the anaerobic methane production system of rubbish from cooking/kitchen garbage, increase biogas output), the wastewater fraction of generation, which can be used for cleaning, to be removed
Miscellaneous, the high COD's in part needs into sewage disposal system；Solid product is the desirable feedstock for cracking liquefaction, for producing
Bunker oil more than CST180 standards can increase fractionating column if scale is more than 50,000 tons every year, produce added value higher
Gasoline, light diesel fuel and bunker oil.
The schematic diagram only shows the combination of 3 reactors, but this method be suitable for 2 only reach more than reactor, this
Needs depending on user.
Mixed plastic is sent into the continuous of isolation air by the mixed plastic isolated after drying, by double-spiral feeder
Formula heat scission reaction kettle under molecular sieve catalyst Y-zeolite catalysis, through reaction in 30 minutes, is converted at 420 DEG C
The cracked oil of high-quality reaches the quality of CST180 bunker oil standards or more, shown in table 1 specific as follows：
Table 1
Comparative example 1
The mixed waste plastic rubbish of mixing after the cleaning removal of impurities of embodiment 1 is directly subjected to cracking system as described in Example 1
Oil reaction, the product of the direct thermal cracking of mixed plastic, overall mechanical impurity content height be unsatisfactory for CST180 standards requirement, need by
The pale yellow powder that PET thermal crackings generate filters out, and the solid residue that this Partial filtration goes out (using organic acid as main component)
There is intense irritation smell to be difficult to be utilized.PET generates a large amount of solid phase organic acids under the above cracking conditions；PVC thermal cracking meetings
Generate byproduct hydrogen chloride.The organic acid and hydrogen chloride product that more importantly PET and PVC thermal crackings generate, will be to catalyst
Service life adversely affect, and have a corrosiveness to cracking apparatus, water in the byproduct hydrogen chloride and material of especially PVC cracking
Divide plus thermogenetic vapor combines, has strong corrosive to equipment.Organic acid and hydrogen chloride, which remain in oily product, can also influence
The quality of oil, stability and its utilization.
Comparative example 1 is it can be seen that through the invention, and first, mixed plastic and organic matter in oversize obtain most
The recycling of big degree, and its product TA, bunker oil quality and biogas quality are good, added value is high；Second, for sieve
Mixed plastic part in upper object, compound pyrohydrolysis+cracking oil-producing technique efficiently avoid PET and PVC pyrolysis products pair and set
It is standby and catalyst to seriously affect, TA products are increased, and make 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 solution, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art answer
Work as understanding：It is still possible to modify or equivalently replace the present invention, without departing from the spirit and scope of the present invention any
Modification or part are replaced, and should all be covered in protection scope of the present invention.
Claims (13)
1. a kind of method using mixed waste plastic junk-free liquefaction, described method includes following steps：
(1) under conditions of temperature is 160~300 DEG C and pressure is 20~220bar, using alkaline aqueous solution to mixing useless modeling
Expect that rubbish carries out pyrohydrolysis processing；
The mixed waste plastic rubbish is containing one or more of PE, PP, PS and PET and PVC；
(2) water phase in the material after hydro-thermal process is detached with solid phase, isolated solid phase is subjected to liquefaction.
2. according to the method described in claim 1, wherein, the mixed waste plastic rubbish contains PE, PP, PS, PET and PVC.
3. according to the method described in claim 1, wherein, the alkaline aqueous solution is selected from Ca (OH)2Aqueous solution, Ba (OH)2It is water-soluble
It is one or more in liquid, KOH aqueous solutions, NaOH aqueous solutions and CsOH aqueous solutions.
4. according to the method described in claim 3, wherein, the alkaline aqueous solution is NaOH aqueous solutions.
5. according to the method described in claim 3, wherein, a concentration of 0.3mol/L~1.7mol/L of the alkaline aqueous solution.
6. according to the method described in claim 3, wherein, the volume matter of the alkaline aqueous solution and the mixed waste plastic rubbish
Amount is than being 2~5L:1Kg.
7. according to the method described in claim 1, wherein, the liquefaction is cracking liquefaction.
8. according to the method described in claim 7, wherein, the cracking liquefaction includes the following steps：
The isolated solid phase of step (2) is sent 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.
9. according to the method described in claim 1, wherein, when containing PS and PE and/or PP in the mixed waste plastic rubbish
When, using density-sorting methods by solid phase obtained by step (2) PS and PE and/or PP divide and open, using PE and/or PP liquefactions, make
It is granulated with PS.
10. method according to claim 1 to 9, wherein in water phase isolated in step (2)
Fining end is divided into raw material and prepares terephthalic acid powder or particle, recycles the recyclable profit of the waste water containing ethylene glycol after terephthalic acid (TPA)
With, then enter back into anaerobic system production natural pond.
11. method according to claim 1 to 9, wherein will be in water phase isolated in step (2)
Muddy part is used for anaerobic methane production by filtering and cake dewatering, by filter cake part, and the waste water separated is Ke Xunhuanliyong.
12. method according to claim 1 to 9, wherein the mixed waste plastic rubbish includes house refuse
Or the preprocessed plastics and dross isolated of plastics or kitchen garbage isolated after rubbish from cooking oversize, compost；
When the mixed waste plastic rubbish be house refuse or rubbish from cooking oversize, the method includes to the oversize into
Row pre-treatment, the pre-treatment include to oversize carry out crushing and screening, to remove the inorganic matter in the oversize, then into
Row cleaning removal of impurities, to remove the grease and organic matter of mixed plastic adhesive surface.
13. according to the method for claim 12, wherein the mixed waste plastic rubbish is that house refuse or rubbish from cooking are sieved
Upper object.
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| KR20220133296A (en) * | 2020-02-10 | 2022-10-04 | 이스트만 케미칼 컴파니 | Apparatus and method for handling particulate plastic solids |
| JP2023532532A (en) | 2020-06-30 | 2023-07-28 | 中国石油化工股▲ふん▼有限公司 | Methods and systems for processing plastic waste materials |
| CN115463649A (en) * | 2021-06-11 | 2022-12-13 | 华南师范大学 | Waste plastic biological resource conversion material and preparation method and application thereof |
| CN114214079A (en) * | 2021-07-28 | 2022-03-22 | 巨锋 | Garbage recycling treatment method based on critical hydrolysis |
| CN116000047B (en) * | 2021-10-22 | 2024-11-12 | 中国石油化工股份有限公司 | A combined pretreatment method and system for waste plastics |
| AT526157B1 (en) * | 2022-07-07 | 2023-12-15 | Denkgruen Energie Und Ressourcen Gmbh | Process for producing fuel gas and/or synthesis gas |
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