CN109705985A - A kind of method that PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon - Google Patents
A kind of method that PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon Download PDFInfo
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Abstract
The present invention relates to a kind of fibers for manufacturing discarded polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT) (PBT), film, the method that plastic bottle is converted into aviation kerosine range cyclic hydrocarbon.This method can with biomass oxygenatedchemicals together hydrogenation deoxidation, obtain simultaneously containing chain hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbons fuel.It solves in the biomass aviation fuel that the prior art obtains due to lacking aromatic hydrocarbons so as to cause the drawback of volume calorific value and leakproofness deficiency.Because film, plastic bottle is not only low in cost using the fiber of discarded PET, PTT, PBT manufacture, but also the fiber of waste PET, PTT, PBT manufacture, film, plastic bottle have very big threat to environment as a kind of white garbage.Therefore this method not only solves the problems, such as aviation fuel to a certain extent, also solves the environmental problem as caused by white pollution.There is potential advantage in following industrial application.
Description
Technical field
The present invention relates to the methods that a kind of PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon.Specifically
Including three steps: 1) fiber for manufacturing waste PET, PTT, PBT, film, alcoholysis at high temperature after plastic bottle is mixed with alcohol
Obtain unsaturated ester；2) ester of the hydrogenation reaction to be saturated is carried out by the beta-unsaturated esters generated to step 1；It 3) will step
The rapid 2 saturated ester hydrogenation deoxidations generated obtain C7-8Aromatic hydrocarbons and alkane.This is to be reported for the first time by waste PET, PTT, PBT at present
The fiber of manufacture, film, the method that plastic bottle is directly transformed into aviation fuel, compared with traditional aviation fuel, raw material comes
Source is cheap and easy to get, and the fiber for PET, PTT, PBT manufacture discarded in life, film, plastic bottle does not need pretreatment can be direct
It uses.
Background technique
Fossil resource is increasingly reduced and by environmental problems such as a large amount of rows of the caused greenhouse gases of fossil energy burning
It becomes increasingly conspicuous, the social required quantity of the energy is also continuing to increase in addition, and oil price rises steadily, and develops alternative fossil resource
New energy, open up renewable fuel supply new channel it is imperative.
The strategic goods and materials national as one, the international demand amount of aviation kerosine are also increasingly increasing.Aviation kerosine one
As be made of alkane of the carbon number between 6~16.The composition of JP-8 common at present is as follows: the linear paraffin that carbon number is 8~15
Accounting for about 35%, the branched paraffin that carbon number is 8~15 accounts for about 35%, and the aromatic hydrocarbon that carbon number is 7~10 accounts for about 18%, and carbon number is 6~
10 cycloalkane accounts for about 7%.From the aspect of national energy security and potential economic value two, renewable boat is greatly developed
Empty kerosene technology has far-reaching strategic importance.The biological aviation kerosine that the prior art synthesizes in the world at present is in chemical structure
Mainly based on chain hydrocarbon, traditional aviation kerosine (chain hydrocarbon, cycloalkane, virtue are lower than in terms of density (volume calorific value) and leakproofness
The mixture of hydrocarbon), it needs to be used in mixed way the performance requirement that can be only achieved aviation fuel with traditional aviation kerosine.
With the rapid development of the national economy, plastics industry achieves development at full speed, plastic material is excellent by its
Performance is favored by every field.At this stage, waste plastic increases year by year, how to be carried out based on using energy source and environmental protection
Waste plastic processing, becomes the focal issue of social concerns.The reasonable disposition of waste plastic and safe handling problem belong to the world
Property environmental issue improve living environment quality for the fundamental state policy for implementing environmental protection, carry out waste plastic environmental protection treatment work
Skill technical research is particularly significant.China is waste plastic big producer, and it is extremely urgent to carry out garbage as resource processing.China is discarded
Plastics are mainly derived from: plastic bag, agricultural and household plastic film, foam, life and industrial plastic product etc..According to incomplete
Statistics, annual China's plastics-production amount are up to ten million ton, year waste plastic amount account for 6 one-tenth or so, and in increasing trend year by year.This
Outside, the overwhelming majority is engineering waste plastic in waste plastic, and since its is many kinds of, enormous amount, is made to society and environment
At huge pressure.
The recycling of waste plastic at present and utilization are mainly the following method: 1) simple recovery processing, waste plastic
Simple recovery processing refers to by carrying out classification recycling to production and domestic waste plastics, and then is directly utilized or processed life
It produces and recycles.The simple recovery processing of waste plastic is most positive material egr mode, is at most effective environmental protection
Reason method.2) composite regenerated processing, composite regenerated processing receives the waste plastic carried out in face of market and handles work, by market
The plastics that the circulation of the production and living such as upper business, industry, agricultural, civilian generates carry out reclaiming work.Specifically include that shearing,
The processes such as roll, remold,.The composite regenerated production cost for not only effectively reducing manufacturing enterprise of waste plastic protects environment
Shield plays the role of more outstanding.3) sanitary landfills is handled, and waste plastic landfill is the smallest processing mode of added value, not only
The circulation value for wasting waste plastic, also occupies the resource in soil in large area, in addition, there is still a need for one for sanitary landfills processing
Fixed safe practice.4) incineration method recycles heat, and waste plastic is the higher fuel of calorific value, and waste plastic is recycled by incineration method
Heat is the higher processing mode of added value, but to handle secondary pollution problem well.Therefore, it is necessary to plastics to carry out it is different at
The screening divided, and need to install additional incineration tail gas processing unit.5) photodegradation technology refers to that addition promotees light during plastics-production
Decomposed substance, such as photosensitizer etc. carry out resolution process to plastics by light.It is containing metal that photodegradation technology, which is mainly dealt with objects,
Plastic products, and then reduce pollution of the heavy metal to water body, air or soil.6) biochemical method processing technique, by locating in advance
Starch and related substances are added in waste plastic after reason, are handled using microorganism, and essentially consisting in reduces plastic strength, drop
Low harmful substance content.But biological decomposition processing requirement is higher, higher cost, and there are no universal uses.7) method of chemical treatment, one
As by waste plastic by pyrolysis, alcoholysis, be hydrolyzed into some small molecules, then the further trans-utilization of these small molecules is obtained
The higher product of economic value added.PET resin is one of current five large-engineering plastics common in the world.PET plastic have compared with
It high film forming and becomes second nature, good optical transparence, excellent abrasion performance frictional property and dimensional stability and electrical insulating property.
The bottle that PET is made into have intensity is big, the transparency is good, nontoxic, impermeable, light weight, production efficiency height etc. thus receive extensively
Application.So far, there are no the relevant reports using discarded PET resin synthesis aviation kerosine range cyclic hydrocarbon in the world.
DMT is obtained after PET alcoholysis.The present invention passes through catalyzed conversion selectivity synthesis C using discarded PET, PTT, PBT resin7-C8Boat
Empty kerosene range cyclic hydrocarbon, can not only turn waste into wealth, reduce environmental pollution, and can also couple, solve with existing biological aviation kerosine
Certainly at present biological aviation kerosine with traditional aviation kerosine compared in terms of volume calorific value and leakproofness there are the problem of, with very
Important practical value.
Summary of the invention
It is an object of that present invention to provide the sides that a kind of PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon
Method
The present invention is achieved by the following technical solutions:
Mainly be accomplished by the following way: PET, PTT, PBT manufacture object are discarded polyethylene terephthalate, gather
Propylene glycol ester terephthalate, polybutylene terephthalate (PBT) manufacture fiber, film, one or both of plastic bottle with
On, it is characterised in that:
Alcoholysis at high temperature after PET, PTT, PBT manufacture object are mixed with alcohol, obtains unsaturated ester, will then obtain
Beta-unsaturated esters are converted into the aliphatic ester of saturation under the catalysis of hydrogenation catalyst, and finally the aliphatic ester of obtained saturation exists
C is converted under the catalysis of hydrogenation deoxidation catalyst7-C8Aviation kerosine range aromatic hydrocarbons and alkane.
The alcohol are as follows: one or more of methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, propylene glycol, butanediol,
It is 10~0.01 that PET, PTT, PBT, which manufacture object and the mass ratio of alcohol,.
The hydrogenation catalyst: carrier is active carbon, silica, aluminium oxide, titanium oxide, zirconium oxide, molecular sieve supported
It is Pt metal, Ru, Pd, Rh, Ir catalyst and Raney's nickel, thunder Buddhist nun cobalt, raney iron, one or more kinds of in thunder Buddhist nun's ketone；It is described
Hydrogenation deoxidation catalyst: silica, active carbon, aluminium oxide, titanium oxide, zirconium oxide, molecular sieve supported Ru-Cu, Ru-Fe, Ru-
One or more of Co, Ru-Ni, Pt-Cu, Rh-Cu, Pd-Cu, Ir-Cu bimetallic catalyst.
Hydrogenation catalyst uses the mode of incipient impregnation to prepare: by containing mass concentration for 0.01%~50% metal
Solution and carrier stand 4~12h at normal temperature after mixing, then dry 4~12h at 60~140 DEG C, then 200
(preferably 500~600 DEG C) roasting 1~12h (preferably 4~7h) at~600 DEG C, in 100~600 DEG C of (preferably 300~500 DEG C) hydrogen
1~6h (preferably 2~4h) is restored under gas atmosphere, finally in the O that volume ratio is 0.1%~10% (preferably 1%)2/N2Gaseous mixture
0.5~12h (preferably 4h) is passivated under atmosphere；
Hydrogenation deoxidation catalyst uses the mode of co-impregnation to prepare: by containing mass concentration for 0.01%~50% it is a variety of
Metallic solution and carrier stand 4~12h at normal temperature after mixing, and then dry 4~12h at 60~140 DEG C, then exists
Under 200~600 DEG C (preferably 500~600 DEG C) roast 1~12h (preferably 4h or more), 100~600 DEG C (preferably 400 DEG C with
On) under hydrogen atmosphere reduction 1~6h preferred recovery time be 1.5~3.5h.
The hydrogenation catalyst: the mass ratio of active metal and carrier is within 0.001~0.5；
The hydrogenation deoxidation catalyst: the mass ratio of active metal and carrier within 0.001~0.6, active metal it
Between mass ratio 0.001~1000.
For hydrogenation catalyst: the mass ratio of active metal and carrier is within 0.01~0.2；
For hydrogenation deoxidation catalyst: the mass ratio of active metal and carrier is within 0.01~0.2, between active metal
Mass ratio within 0.25~6.
For alcoholysis process: alcoholysis reaction carries out in a kettle, and reaction temperature is at 100~300 DEG C, preferable reaction temperature
It is 200 DEG C~260 DEG C, the reaction time is 0.5~10 hour, and preferred reaction time is 4~10 hours；
For hydrogenation process: hydrogenation reaction carries out in a kettle, and reaction temperature is at 50~300 DEG C, preferable reaction temperature
It is 120~260 DEG C, the mass ratio of catalyst and beta-unsaturated esters is 0.01~0.5, and the reaction time is 0.5~24 hour, preferably instead
16~24 hours between seasonable, Hydrogen Vapor Pressure is in 0.1~8MPa, preferably 2~8MPa of Hydrogen Vapor Pressure；
For hydrogenation deoxidation process: hydrogenation deoxidation reaction is carried out in fixed bed, reaction temperature between 150~550 DEG C,
Preferable reaction temperature is 450~500 DEG C, and Hydrogen Vapor Pressure is in 0.1~8MPa, preferably 4~8MPa of Hydrogen Vapor Pressure, catalyst quality
1~3g, the flow velocity of saturated ester are 0.001~3ml/min, and preferable flow rate is 0.01~0.1ml/min, hydrogen flow rate is 60~
200ml/min, preferable flow rate are 150~200ml/min.
The present invention has the advantage that
The method provided by the present invention that PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon, tool
Have the characteristics that raw material is cheap and easy to get, synthetic method is simple, substrate universality is high, and traditional biomass aviation kerosine can be obtained and lacked
Few aromatic component, and aromatic hydrocarbons is the necessary component of aviation kerosine.On the other hand, this method can subtract from the aspect of environment
Few white pollution, not only solves energy problem to a certain extent, also solves environmental problem on determining degree.Therefore it is this quite
With prospects.
Detailed description of the invention
The chemical structural drawing of Fig. 1 waste plastic bottle (being from top to bottom respectively PET, PTT, PBT).
Fig. 2-5 is the chemical structural drawing of series of intermediate products, as follows in detail: Fig. 2 is dimethyl terephthalate (DMT) (DMT)
Chemical structural drawing；Fig. 3 is the chemical structural drawing of diethyl terephthalate；Fig. 4 is the chemistry knot of terephthalic acid (TPA) dipropyl
Composition；Fig. 5 is the chemical structural drawing of dibutyl terephthalate；Fig. 6 is the change of 1,4- cyclohexane diacid dimethyl phthalate (DMCD)
Learn structure chart.
Fig. 7-14 is the chemical structural drawing of final aviation fuel component, as follows in detail: Fig. 7 is Isosorbide-5-Nitrae-dimethyleyelohexane alkanisation
Learn structure chart；Fig. 8 is 1,3- dimethyl cyclohexane chemical structural drawing；Fig. 9 is 1,2- dimethyl cyclohexane chemical structural drawing；Figure 10
For hexahydrotoluene chemical structural drawing；Figure 11 is that paraxylene knot is chemically patterned；Figure 12 is that ortho-xylene knot is chemically patterned；Figure 13
It is chemically patterned for meta-xylene knot；Figure 14 is toluene chemical structural drawing.
Specific embodiment
The present invention will be illustrated with specific embodiment below, but protection scope of the present invention is not limited to these
Example.
Embodiment
1. the preparation of catalyst:
Hydrogenation catalyst is prepared by the way of incipient impregnation: will be mixed with carrier containing a certain amount of metallic solution
4~12h is stood after even at normal temperature, then dry 4~12h at 60~120 DEG C, then at 200~600 DEG C roasting 1~
6h restores 1~6h under 100~400 DEG C of hydrogen atmospheres, the O for being finally 1% in volume ratio2/N2Mixed atmosphere under be passivated 4h.
Embodiment see the table below
Hydrogenation deoxidation catalyst is prepared by the way of co-impregnation: will be mixed containing a certain amount of various metals solution with carrier
4~12h is stood at normal temperature after closing uniformly, and then dry 4~12h at 60~120 DEG C, then roasts at 200~600 DEG C
1~6h restores 1~6h under 100~400 DEG C of hydrogen atmospheres, the O for being finally 1% in volume ratio2/N2Mixed atmosphere under be passivated
4h.Embodiment see the table below 2. investigation dimethyl terephthalate (DMT)s (DMT) plus hydrogen to 1,4- cyclohexane diacid dimethyl phthalate (DMCD)
The activity for the catalyst for hydrogenation that different preparation methods obtain in the process.Reaction condition: 30g DMT, 1g catalyst, hydrogen pressure
Power: 5MPa, reaction temperature: 100 DEG C, the reaction time: 7h.It is shown in Table 1-9
The catalyst of 1. different metal of table load
Note: prepared catalyst use the following conditions preparation in table 1: by containing concentration of metal ions for 5% solution
8h is stood at normal temperature after mixing with 1g carrier, and the mass ratio control of metal ion and carrier is 5%, then at 120 DEG C
Lower dry 10h, then roasts 4h at 500 DEG C, the reductase 12 h under 300 DEG C of hydrogen atmospheres, the O for being finally 1% in volume ratio2/N2
Mixed atmosphere under be passivated 4h.
As seen from Table 1, the activated-carbon catalyst of different metal load has the catalytic activity of this hydrogenation process very big
Difference, wherein metal platinum have highest conversion ratio and yield.
Influence of the 2. different metal load capacity of table to catalyst activity
| Embodiment | Load capacity (wt.%) | DMT conversion ratio (%) | DMCD yield (%) |
| Embodiment 10 | 0.1 | 2.9 | 1.8 |
| Embodiment 11 | 0.2 | 6.4 | 5.2 |
| Embodiment 12 | 0.5 | 12.1 | 8.8 |
| Embodiment 13 | 1 | 21.3 | 18.9 |
| Embodiment 14 | 2 | 42.0 | 39.6 |
| Embodiment 15 | 5 | 82.1 | 79.5 |
| Embodiment 16 | 6 | 83.2 | 81.6 |
| Embodiment 17 | 7 | 82.6 | 80.9 |
| Embodiment 18 | 8 | 82.2 | 79.2 |
| Embodiment 19 | 9 | 80.9 | 80.1 |
| Embodiment 20 | 10 | 81.5 | 79.9 |
| Embodiment 21 | 20 | 82.2 | 79.1 |
| Embodiment 22 | 30 | 83.3 | 82.6 |
| Embodiment 23 | 40 | 81.6 | 80.0 |
| Embodiment 24 | 50 | 80.2 | 79.5 |
| Embodiment 25 | 60 | 81.9 | 81.1 |
Note: prepared catalyst uses the following conditions to prepare in table 2: will be containing platinum ion concentration for 5% solution and 1g
Carrier stands 8h at normal temperature after mixing, and then the dry 10h at 120 DEG C, then roasts 4h at 500 DEG C, at 300 DEG C
Reductase 12 h under hydrogen atmosphere, the O for being finally 1% in volume ratio2/N2Mixed atmosphere under be passivated 4h.
From table 2 it can be seen that with the increase of content of metal, the activity of catalyst is gradually increased, but when load capacity mentions
Height to not just being further added by after 5%, show in a certain range, with its activity over catalysts position of the increase of content of metal also by
It is cumulative to add.
Influence of the different time of repose of table 3. to synthesized catalytic activity
| Embodiment | Time (h) | DMT conversion ratio (%) | DMCD yield (%) |
| Embodiment 26 | 1 | 65.1 | 60.8 |
| Embodiment 27 | 2 | 69.3 | 65.2 |
| Embodiment 28 | 3 | 72.1 | 70.4 |
| Embodiment 29 | 4 | 79.3 | 77.6 |
| Embodiment 30 | 5 | 81.2 | 80.0 |
| Embodiment 31 | 6 | 80.3 | 78.8 |
| Embodiment 32 | 7 | 81.5 | 79.6 |
| Embodiment 33 | 8 | 82.1 | 79.5 |
| Embodiment 34 | 9 | 80.1 | 79.9 |
| Embodiment 35 | 10 | 81.8 | 80.2 |
| Embodiment 36 | 11 | 81.3 | 80.5 |
| Embodiment 37 | 12 | 80.5 | 80.1 |
| Embodiment 38 | 13 | 80.6 | 79.9 |
Note: prepared catalyst use the following conditions to prepare in table 3: by containing platinum ion concentration for 5% solution and
1g carrier is stood at normal temperature after mixing, and the mass ratio of metal ion and carrier is controlled 5%, is then done at 120 DEG C
Dry 10h then roasts 4h at 500 DEG C, the reductase 12 h under 300 DEG C of hydrogen atmospheres, the O for being finally 1% in volume ratio2/N2It is mixed
It closes and is passivated 4h under atmosphere.
As seen from Table 3, different time of repose have a certain impact to prepared catalytic activity, but time of repose is more than
It is just had little effect after 4 hours.
Influence of the 4. catalyst drying temperature of table to synthesized catalyst activity
Note: prepared catalyst use the following conditions to prepare in table 4: by containing platinum ion concentration for 5% solution and
1g carrier stands 8h at normal temperature after mixing, then the mass ratio control of metal ion and carrier is dried 10h, connect 5%
Roast 4h at 500 DEG C, the reductase 12 h under 300 DEG C of hydrogen atmospheres, finally in volume ratio be 1% O2/N2Mixed atmosphere under
It is passivated 4h.
As can be seen from Table 4, different drying temperatures have a certain impact to the hydrogenation activity of catalyst, but when temperature is super
It is had little effect after crossing 70 DEG C.
Influence of the 5. catalyst drying time of table to synthesized catalyst activity
| Embodiment | Time (h) | DMT conversion ratio (%) | DMCD yield (%) |
| Embodiment 50 | 1 | 71.3 | 62.2 |
| Embodiment 51 | 2 | 72.1 | 67.1 |
| Embodiment 52 | 3 | 81.7 | 79.0 |
| Embodiment 53 | 4 | 82.6 | 78.8 |
| Embodiment 54 | 5 | 81.4 | 79.5 |
| Embodiment 55 | 6 | 81.1 | 80.1 |
| Embodiment 56 | 7 | 80.5 | 79.8 |
| Embodiment 57 | 8 | 81.1 | 80.5 |
| Embodiment 58 | 9 | 81.1 | 80.2 |
| Embodiment 59 | 10 | 81.7 | 79.8 |
| Embodiment 60 | 11 | 83.0 | 81.5 |
Note: prepared catalyst use the following conditions to prepare in table 5: by containing platinum ion concentration for 5% solution and
1g carrier stands 8h at normal temperature after mixing, and the mass ratio control of metal ion and carrier is 5%, then at 120 DEG C
It is dry, 4h then is roasted at 500 DEG C, the reductase 12 h under 300 DEG C of hydrogen atmospheres, the O for being finally 1% in volume ratio2/N2It is mixed
It closes and is passivated 4h under atmosphere.
As can be seen from Table 5, when drying between more than 3 hours after drying time to the active group of prepared catalyst
This is not influenced.
Influence of 6. maturing temperature of table to synthesized catalyst activity
Note: prepared catalyst use the following conditions to prepare in table 6: by containing platinum ion concentration for 5% solution and
1g carrier stands 8h at normal temperature after mixing, and the mass ratio control of metal ion and carrier is 5%, then at 120 DEG C
Dry 10h, then in high-temperature roasting 4h, the reductase 12 h under 300 DEG C of hydrogen atmospheres, the O for being finally 1% in volume ratio2/N2It is mixed
It closes and is passivated 4h under atmosphere.
As can be seen from Table 6, maturing temperature has significant impact to catalyst activity, as the temperature rises, catalysis
The activity of agent significantly improves, and is held essentially constant after more than 500 degree.
Influence of 7. calcining time of table to synthesized catalyst activity
| Embodiment | Time (h) | DMT conversion ratio (%) | DMCD yield (%) |
| Embodiment 70 | 1 | 36.5 | 33.9 |
| Embodiment 71 | 2 | 57.1 | 54.1 |
| Embodiment 72 | 3 | 71.7 | 66.3 |
| Embodiment 73 | 4 | 81.5 | 79.6 |
| Embodiment 74 | 5 | 81.2 | 80.0 |
| Embodiment 75 | 6 | 81.3 | 78.8 |
| Embodiment 76 | 7 | 80.5 | 79.4 |
| Embodiment 77 | 8 | 74.2 | 71.2 |
| Embodiment 78 | 9 | 67.6 | 60.9 |
| Embodiment 79 | 10 | 56.4 | 52.9 |
| Embodiment 80 | 11 | 46.9 | 43.0 |
| Embodiment 81 | 12 | 32.5 | 22.8 |
Note: prepared catalyst use the following conditions to prepare in table 7: by containing platinum ion concentration for 5% solution and
1g carrier stands 8h at normal temperature after mixing, and the mass ratio control of metal ion and carrier is 5%, then at 120 DEG C
Dry 10h, the then high-temperature roasting at 500 DEG C, the reductase 12 h under 300 DEG C of hydrogen atmospheres, the O for being finally 1% in volume ratio2/N2
Mixed atmosphere under be passivated 4h.
As can be seen from Table 7, in 1 to 4 hours, with the increase of calcining time, catalyst activity is gradually increased, 4
To in 7 hours, even if increasing calcining time, catalyst activity is also held essentially constant.And upon firing between extend to 7 hours
Afterwards, catalyst activity is gradually decreased with the extension of calcining time.
Influence of 8. catalyst reduction temperature of table to synthesized catalyst activity
| Embodiment | Temperature (DEG C) | DMT conversion ratio (%) | DMCD yield (%) |
| Embodiment 82 | 100 | 33.2 | 30.0 |
| Embodiment 83 | 150 | 58.4 | 54.6 |
| Embodiment 84 | 200 | 71.1 | 69.8 |
| Embodiment 85 | 250 | 79.4 | 76.3 |
| Embodiment 86 | 300 | 81.5 | 79.6 |
| Embodiment 87 | 350 | 80.8 | 79.7 |
| Embodiment 88 | 400 | 80.4 | 79.8 |
| Embodiment 89 | 450 | 80.5 | 79.6 |
| Embodiment 90 | 500 | 81.8 | 80.7 |
| Embodiment 91 | 550 | 79.9 | 79.3 |
Note: prepared catalyst use the following conditions to prepare in table 8: by containing platinum ion concentration for 5% solution and
1g carrier stands 8h at normal temperature after mixing, and the mass ratio control of metal ion and carrier is 5%, then at 120 DEG C
10h is dried, then the high-temperature roasting 4h at 500 DEG C, in a hydrogen atmosphere reductase 12 h, the O for being finally 1% in volume ratio2/N2's
4h is passivated under mixed atmosphere.
As can be seen from Table 8, with the raising of catalyst reduction temperature, catalyst activity is gradually increased, when temperature increases
To after 250 DEG C, catalyst reduction temperature does not influence its activity substantially.
Influence of the 9. catalyst reduction time of table to synthesized catalyst activity
| Embodiment | Time (h) | DMT conversion ratio (%) | DMCD yield (%) |
| Embodiment 92 | 0.5 | 38.9 | 37.0 |
| Embodiment 93 | 1 | 51.4 | 48.6 |
| Embodiment 94 | 1.5 | 73.2 | 70.1 |
| Embodiment 95 | 2 | 81.5 | 79.6 |
| Embodiment 96 | 2.5 | 79.7 | 79.3 |
| Embodiment 97 | 3 | 81.0 | 79.7 |
| Embodiment 98 | 3.5 | 81.5 | 79.9 |
Note: prepared catalyst use the following conditions to prepare in table 9: by containing platinum ion concentration for 5% solution and
1g carrier stands 8h at normal temperature after mixing, and the mass ratio control of metal ion and carrier is 5%, then at 120 DEG C
Dry 10 hours, then high-temperature roasting 4 hours at 500 DEG C, restored under 300 DEG C of hydrogen atmospheres, finally in volume ratio be 1%
O2/N2Mixed atmosphere under be passivated 4h.
As can be seen from Table 9, with the raising from the catalyst reduction time, catalyst activity is continuously improved.3.1,4- ring
Hexane diacid dimethyl phthalate (DMCD) hydrogenation deoxidation is to C7-C8The hydrogenation deoxidation reaction that different preparation methods obtain during hydrocarbon is urged
The activity of agent.Hydrogenation deoxidation reaction carries out in fixed bed, and reaction temperature is at 400 DEG C, and Hydrogen Vapor Pressure is in 4MPa, catalyst matter
Amount is 1.8g, and the flow velocity of saturated ester is 0.04ml/min, hydrogen flow rate 120ml/min.It is shown in Table 10-18
The catalyst of 10. different metal of table load
Note: prepared catalyst is prepared using the following conditions in table 10: will be containing there are many molten of 5% concentration of metal ions
Liquid and 1g carrier stand 8h at normal temperature after mixing, and the mass ratio control of metal ion and carrier is 5%, then 120
Dry 10h, then roasts 4h at 500 DEG C, the reductase 12 h under 400 DEG C of hydrogen atmospheres at DEG C.
As seen from Table 10, the catalyst of different metal load has the catalytic activity of this hydrogenation deoxidation process very big
Difference, wherein ruthenium copper bimetallic catalyst has highest conversion ratio and yield.
Influence of the 11. different metal load capacity of table to catalyst activity
Note: prepared catalyst is prepared using the following conditions in table 11: will contain ruthenium, copper ion mass concentration each 5%
Solution and 1g carrier stand 8h at normal temperature after mixing, then the dry 10h at 120 DEG C, then roasts at 500 DEG C
4h, the reductase 12 h under 400 DEG C of hydrogen atmospheres.
As can be seen from Table 11, with metal Ru load capacity increase to 2wt.% after, the conversion ratio of DMCD reaches maximum
Value, but C7-C8Cyclic hydrocarbon yield is not highest really, and the only C when the mass ratio of ruthenium and copper is close to 17-C8Cyclic hydrocarbon yield
Highest.
Influence of the different time of repose of table 12. to synthesized catalytic activity
| Embodiment | Time (h) | DMCD conversion ratio (%) | C7-C8Yield (%) |
| Embodiment 124 | 1 | 85.1 | 70.8 |
| Embodiment 125 | 2 | 99.3 | 95.2 |
| Embodiment 126 | 3 | 98.1 | 90.4 |
| Embodiment 127 | 4 | 99.3 | 97.6 |
| Embodiment 128 | 5 | 98.2 | 94.0 |
| Embodiment 129 | 6 | 97.3 | 92.8 |
| Embodiment 130 | 7 | 99.5 | 94.6 |
| Embodiment 131 | 8 | 98.1 | 96.5 |
| Embodiment 132 | 9 | 99.1 | 94.9 |
| Embodiment 133 | 10 | 98.8 | 90.2 |
| Embodiment 134 | 11 | 99.3 | 94.5 |
| Embodiment 135 | 12 | 99.5 | 95.1 |
| Embodiment 136 | 13 | 98.6 | 95.9 |
Note: prepared catalyst is prepared using the following conditions in table 12: will contain ruthenium, copper ion mass concentration each 5%
Solution stood at normal temperature after mixing with 1g carrier, the mass ratio of each metal ion and carrier is controlled 5%, is then existed
Dry 10h, then roasts 4h at 500 DEG C, the reductase 12 h under 400 DEG C of hydrogen atmospheres at 120 DEG C.
As seen from Table 12, different time of repose have a certain impact to prepared catalytic activity, but time of repose is super
It is just had little effect after spending 2 hours.
Influence of the 13. catalyst drying temperature of table to synthesized catalyst activity
Note: prepared catalyst is prepared using the following conditions in table 13: will contain ruthenium, copper ion mass concentration each 5%
Solution and 1g carrier stand 8h at normal temperature after mixing, 5%, then the mass ratio of each metal ion and carrier controls
Dry 10h, then roasts 4h at 500 DEG C, the reductase 12 h under 400 DEG C of hydrogen atmospheres.
As can be seen from Table 13, different drying temperatures have a certain impact to the hydrogenation activity of catalyst, but work as temperature
It is had little effect after more than 70 DEG C.
Influence of the 14. catalyst drying time of table to synthesized catalyst activity
Note: prepared catalyst is prepared using the following conditions in table 14: will contain ruthenium, copper ion mass concentration each 5%
Solution and 1g carrier stand 8h at normal temperature after mixing, 5%, then the mass ratio of each metal ion and carrier controls
It is dry at 120 DEG C, 4h then is roasted at 500 DEG C, the reductase 12 h under 400 DEG C of hydrogen atmospheres.
As can be seen from Table 14, when drying between more than 3 hours after drying time to the activity of prepared catalyst
Substantially it does not affect.
Influence of 15. maturing temperature of table to synthesized catalyst activity
Note: prepared catalyst is prepared using the following conditions in table 15: will contain ruthenium, copper ion mass concentration each 5%
Solution and 1g carrier stand 8h at normal temperature after mixing, 5%, then the mass ratio of each metal ion and carrier controls
The dry 10h at 120 DEG C, then in high-temperature roasting 4h, the reductase 12 h under 400 DEG C of hydrogen atmospheres.
As can be seen from Table 15, maturing temperature has significant impact to catalyst activity, as the temperature rises, catalysis
The activity of agent significantly improves, and is held essentially constant after more than 500 DEG C.
Influence of 16. calcining time of table to synthesized catalyst activity
| Embodiment | Time (h) | DMCD conversion ratio (%) | C7-C8Cyclic hydrocarbon yield (%) |
| Embodiment 167 | 1 | 56.5 | 43.9 |
| Embodiment 168 | 2 | 77.1 | 74.1 |
| Embodiment 169 | 3 | 91.7 | 86.3 |
| Embodiment 170 | 4 | 98.1 | 96.5 |
| Embodiment 171 | 5 | 99.2 | 92.0 |
| Embodiment 172 | 6 | 99.3 | 91.8 |
| Embodiment 173 | 7 | 99.5 | 95.4 |
| Embodiment 174 | 8 | 99.2 | 94.2 |
| Embodiment 175 | 9 | 99.6 | 96.9 |
| Embodiment 176 | 10 | 99.4 | 95.9 |
| Embodiment 177 | 11 | 99.9 | 98.0 |
| Embodiment 178 | 12 | 99.5 | 92.8 |
Note: prepared catalyst is prepared using the following conditions in table 16: will contain ruthenium, copper ion mass concentration each 5%
Solution and 1g carrier stand 8h at normal temperature after mixing, 5%, then the mass ratio of each metal ion and carrier controls
Dry 10h, the then high-temperature roasting at 500 DEG C, the reductase 12 h under 400 DEG C of hydrogen atmospheres at 120 DEG C.
As can be seen from Table 16, in 1 to 4 hours, with the increase of calcining time, catalyst activity is gradually increased, 4
To in 12 hours, even if increasing calcining time, catalyst activity is also held essentially constant.
Influence of 17. catalyst reduction temperature of table to synthesized catalyst activity
Note: prepared using the following conditions will be containing ruthenium, copper ion mass concentration each 5% for prepared catalyst in table 17
Solution and 1g carrier stand 8h at normal temperature after mixing, then the mass ratio control of each metal ion and carrier exists 5%
10h is dried at 120 DEG C, then the high-temperature roasting 4h at 500 DEG C, in a hydrogen atmosphere reductase 12 h.
As can be seen from Table 17, with the raising of catalyst reduction temperature, catalyst activity is gradually increased, when temperature increases
To after 350 degree, catalyst reduction temperature does not influence its activity substantially.
Influence of the 18. catalyst reduction time of table to synthesized catalyst activity
| Embodiment | Time (h) | DMCD conversion ratio (%) | C7-C8Cyclic hydrocarbon yield (%) |
| Embodiment 189 | 0.5 | 38.9 | 37.0 |
| Embodiment 190 | 1 | 51.4 | 48.6 |
| Embodiment 191 | 1.5 | 93.2 | 85.1 |
| Embodiment 192 | 2 | 99.5 | 94.6 |
| Embodiment 193 | 2.5 | 99.7 | 99.3 |
| Embodiment 194 | 3 | 99.0 | 95.7 |
| Embodiment 195 | 3.5 | 99.5 | 99.1 |
Note: prepared catalyst is prepared using the following conditions in table 18: will contain ruthenium, copper ion mass concentration each 5%
Solution and 1g carrier stand 8h at normal temperature after mixing, 5%, then the mass ratio of each metal ion and carrier controls
10 hours dry at 120 DEG C, then high-temperature roasting 4 hours at 500 DEG C, restore under 400 DEG C of hydrogen atmospheres.
As can be seen from Table 18, with the raising from the catalyst reduction time, catalyst activity is continuously improved.4. discarded modeling
Bottle alcoholysis is expected into monomer, and the influence of each reaction condition is shown in Table 19-21.
Influence of 19. different solvents of table to alcoholysis process
| Embodiment | Solvent | Waste plastic bottle conversion ratio (%) | Monomer yield (%) |
| Embodiment 196 | Methanol | 99.1 | 95.0 |
| Embodiment 197 | Ethyl alcohol | 70.1 | 68.8 |
| Embodiment 198 | Propyl alcohol | 61.8 | 60.2 |
| Embodiment 199 | Butanol | 53.3 | 52.9 |
| Embodiment 200 | Ethylene glycol | 99.2 | 95.6 |
| Embodiment 201 | Propylene glycol | 88.6 | 86.1 |
| Embodiment 202 | Butanediol | 79.0 | 76.7 |
Note: the reaction condition in table 19: 1g waste PET plastic bottle, 30ml solvent, 200 DEG C, 3.5h.
As can be seen from Table 19, various alcohol all work to the alcoholysis of waste plastic bottle, but methanol, the effect of ethylene glycol
It is best.
Influence of 20. different temperatures of table to alcoholysis process
| Embodiment | Temperature (DEG C) | Waste plastic bottle conversion ratio (%) | DMT yield (%) |
| Embodiment 203 | 50 | 3.1 | 2.2 |
| Embodiment 204 | 60 | 10.1 | 8.8 |
| Embodiment 205 | 80 | 13.8 | 10.2 |
| Embodiment 206 | 100 | 15.3 | 12.9 |
| Embodiment 207 | 120 | 19.1 | 15.6 |
| Embodiment 208 | 140 | 42.6 | 38.1 |
| Embodiment 209 | 160 | 69.0 | 66.7 |
| Embodiment 210 | 180 | 86.3 | 84.7 |
| Embodiment 211 | 200 | 99.1 | 95.0 |
| Embodiment 212 | 220 | 99.3 | 94.9 |
| Embodiment 213 | 240 | 99.9 | 94.1 |
| Embodiment 214 | 260 | 99.3 | 94.3 |
Note: the reaction condition in table 20: 1g discards PTT plastic bottle, 30ml methanol, 3.5h.
As can be seen from Table 20, it grows as the temperature rises, the alcoholysis degree of waste plastic bottle is higher, until temperature is raised to
After 200 DEG C, alcoholysis is complete for waste plastic bottle.
Influence of 21. reaction time of table to alcoholysis process
Note: the reaction condition in table 21: 1g discards PBT plastic bottle, 30ml methanol, and 200 DEG C.
As can be seen from Table 21, it as the growth in reaction time, the degree of alcoholysis are gradually increased, is kept after 4 hours
It is constant.
5. during adding hydrogen to DMCD by DMT, the influence of reaction condition is shown in Table 22-25.
The influence of influence of 22. catalyst quality of table to this hydrogenation process
Note: the reaction condition in table 22: 30g DMT, 5%Pt/C are catalyst, 100 DEG C, 7h, Hydrogen Vapor Pressure: and 5MPa,
As can be seen from Table 22, with the increase of catalyst quality, the conversion ratio of DMT is gradually increased, until increasing to 3g
It is not just further added by afterwards.
23. influence of the different temperatures to this hydrogenation process
Note: the reaction condition in table 23: 30g DMT, 1g 5%Pt/C, 7h, Hydrogen Vapor Pressure: 5MPa, it can from table 23
Out, it grows as the temperature rises, DMT adds hydrogen more complete, and after temperature is raised to 120 degree, DMT is hydrogenated completely.
Influence of 24. reaction time of table to this hydrogenation process
| Embodiment | Time (h) | DMT conversion ratio (%) | DMCD yield (%) |
| Embodiment 241 | 0.5 | 13.1 | 12.2 |
| Embodiment 242 | 1 | 20.1 | 18.8 |
| Embodiment 243 | 4 | 63.8 | 60.2 |
| Embodiment 244 | 8 | 89.0 | 88.9 |
| Embodiment 245 | 16 | 95.1 | 93.6 |
| Embodiment 246 | 20 | 99.6 | 94.1 |
| Embodiment 247 | 24 | 99.6 | 94.7 |
Note: the reaction condition in table 24: 30g DMT, 1g 5%Pt/C, 100 DEG C, Hydrogen Vapor Pressure: 5MPa, it can be with from table 24
Find out, with the growth in reaction time, the degree of alcoholysis is gradually increased, and is remained unchanged after 20 hours.
Influence of 25. Hydrogen Vapor Pressure of table to this hydrogenation process
Note: the reaction condition in table 25: 30g DMT, 1g 5%Pt/C, 100 DEG C, 7h.
As can be seen from Table 25, Hydrogen Vapor Pressure has significant impact to this hydrogenation process, when pressure is lower than 1MPa, DMT
Conversion ratio it is very low, after pressure is more than 2MPa, the conversion ratio of DMT is improved rapidly.
By DMCD hydrogenation deoxidation to C7-C8During cyclic hydrocarbon, the influence of reaction condition is shown in Table 26-29.
Influence of 26. reaction temperature of table to this hydrogenation deoxidation process
| Embodiment | Temperature (DEG C) | DMCD conversion ratio (%) | C7-C8Cyclic hydrocarbon yield (%) |
| Embodiment 255 | 200 | 31.1 | 2.2 |
| Embodiment 256 | 250 | 40.1 | 8.8 |
| Embodiment 257 | 300 | 73.8 | 30.2 |
| Embodiment 258 | 350 | 97.2 | 68.9 |
| Embodiment 260 | 400 | 98.1 | 96.5 |
| Embodiment 261 | 450 | 99.0 | 98.9 |
| Embodiment 262 | 500 | 99.6 | 98.7 |
Note: the reaction condition in table 26: DMCD flow velocity: 0.04ml/min, 1.8g 2.5wt.%Ru-2.5wt.%Cu/
SiO2, hydrogen flowing quantity: 120ml/min, pressure: 4MPa.
As can be seen from Table 26, reaction temperature has very big influence for this hydrogenation deoxidation process, when temperature is more than 400
After DEG C, continue to increase temperature, DMCD conversion ratio and C7-C8Cyclic hydrocarbon yield all no longer improves.
Influence of the table 27.DMCD flow velocity to this hydrogenation deoxidation process
Note: the reaction condition in table 27: 1.8g 2.5wt.%Ru-2.5wt.%Cu/SiO2, hydrogen flowing quantity: 120ml/
Min, pressure: 4MPa, 400 DEG C.
As can be seen from Table 27 with the raising of DMCD flow velocity, the conversion ratio of DMCD has almost no change.But work as flow velocity
After 1ml/min, the conversion ratio of DMCD is gradually decreased.
Influence of 28. hydrogen flowing quantity of table to this hydrogenation deoxidation process
Note: the reaction condition in table 28: DMCD flow velocity: 0.04ml/min, 1.8g 2.5wt.%Ru-2.5wt.%Cu/
SiO2, pressure: 4MPa, 400 DEG C.
As can be seen from Table 28, hydrogen flow rate has significant impact to word hydrogenation deoxidation process, but when flow is more than
After 80ml/min, hydrogen flowing quantity has little effect reaction.
Influence of 29. Hydrogen Vapor Pressure of table to this hydrogenation deoxidation process
Note: the reaction condition in table 29: DMCD flow velocity: 0.04ml/min, 1.8g 2.5wt.%Ru-2.5wt.%Cu/
SiO2, hydrogen flowing quantity: 120ml/min, 400 DEG C.
As can be seen from Table 29, Hydrogen Vapor Pressure has a great impact to this hydrogenation deoxidation process, when pressure is lower than 4MPa,
The either conversion ratio of DMCD or C7-C8The yield of cyclic hydrocarbon is all lower, and when pressure is more than 4MPa, the conversion ratio of DMCD is still
C7-C8The yield of cyclic hydrocarbon is kept approximately constant.
30. different solvents of table and influence of the waste plastic bottle mass ratio to alcoholysis process
Note: the reaction condition in table 19: 1g waste PET plastic bottle, methanol is as solvent, and 200 DEG C, 3.5h.
As can be seen from the above table, the mass ratio of solvent and plastic bottle increases, and the yield of the conversion ratio of plastic bottle and DMT are all
It gradually rises.
Claims (7)
1. a kind of method that PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon, PET, PTT, PBT manufacture object
It is manufactured for discarded polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate (PBT)
Fiber, film, one or more of plastic bottle, it is characterised in that:
Alcoholysis at high temperature after PET, PTT, PBT manufacture object are mixed with alcohol, obtains unsaturated ester, the insatiable hunger that will then obtain
The aliphatic ester of saturation is converted under the catalysis of hydrogenation catalyst with ester, the aliphatic ester of obtained saturation is finally being added into hydrogen
C is converted under the catalysis of dehydrogenation catalyst7-C8Aviation kerosine range aromatic hydrocarbons and alkane.
2. according to the method described in claim 1, it is characterized by:
The alcohol are as follows: one or more of methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, propylene glycol, butanediol, PET,
It is 10~0.01 that PTT, PBT, which manufacture object and the mass ratio of alcohol,.
3. according to the method described in claim 1, it is characterized by:
The hydrogenation catalyst: carrier is active carbon, silica, aluminium oxide, titanium oxide, zirconium oxide, molecular sieve supported metal
It is Pt, Ru, Pd, Rh, Ir catalyst and Raney's nickel, thunder Buddhist nun cobalt, raney iron, one or more kinds of in thunder Buddhist nun's ketone；
The hydrogenation deoxidation catalyst: silica, active carbon, aluminium oxide, titanium oxide, zirconium oxide, molecular sieve supported Ru-Cu,
One or more of Ru-Fe, Ru-Co, Ru-Ni, Pt-Cu, Rh-Cu, Pd-Cu, Ir-Cu bimetallic catalyst.
4. catalyst according to claim 1 or 3, it is characterised in that:
Hydrogenation catalyst uses the mode of incipient impregnation to prepare: by containing mass concentration for 0.01%~50% metallic solution
4~12h is stood at normal temperature after mixing with carrier, then dry 4~12h at 60~140 DEG C, then 200~600
(preferably 500~600 DEG C) roasting 1~12h (preferably 4~7h) at DEG C, in 100~600 DEG C of (preferably 300~500 DEG C) hydrogen gas
1~6h (preferably 2~4h) is restored under atmosphere, finally in the O that volume ratio is 0.1%~10% (preferably 1%)2/N2Mixed atmosphere under
It is passivated 0.5~12h (preferably 4h)；
Hydrogenation deoxidation catalyst uses the mode of co-impregnation to prepare: by containing mass concentration for 0.01%~50% various metals
Solution and carrier stand 4~12h at normal temperature after mixing, then dry 4~12h at 60~140 DEG C, then 200
1~12h (preferably 4h or more) is roasted under~600 DEG C (preferably 500~600 DEG C), in 100~600 DEG C of (preferably 400 DEG C or more) hydrogen
It is 1.5~3.5h that 1~6h preferred recovery time is restored under gas atmosphere.
5. according to claim 1, catalyst described in 3 or 4, it is characterised in that:
The hydrogenation catalyst: the mass ratio of active metal and carrier is within 0.001~0.5；
The hydrogenation deoxidation catalyst: the mass ratio of active metal and carrier within 0.001~0.6, between active metal
Mass ratio is 0.001~1000.
6. according to claim 1, catalyst described in 3,4 or 5, it is characterised in that:
For hydrogenation catalyst: the mass ratio of active metal and carrier is within 0.01~0.2；
For hydrogenation deoxidation catalyst: matter of the mass ratio of active metal and carrier within 0.01~0.2, between active metal
Ratio is measured within 0.25~6.
7. according to the method described in claim 1, it is characterized by:
For alcoholysis process: alcoholysis reaction carries out in a kettle, and reaction temperature is in 100~300 DEG C, preferable reaction temperature
200 DEG C~260 DEG C, the reaction time is 0.5~10 hour, and preferred reaction time is 4~10 hours；
For hydrogenation process: hydrogenation reaction carries out in a kettle, and reaction temperature is at 50~300 DEG C, preferable reaction temperature 120
~260 DEG C, the mass ratio of catalyst and beta-unsaturated esters is 0.01~0.5, and the reaction time is 0.5~24 hour, when preferably reacting
Between 16~24 hours, Hydrogen Vapor Pressure is in 0.1~8MPa, preferably 2~8MPa of Hydrogen Vapor Pressure；
For hydrogenation deoxidation process: hydrogenation deoxidation reaction carries out in fixed bed, and reaction temperature is between 150~550 DEG C, preferably
Reaction temperature is 450~500 DEG C, Hydrogen Vapor Pressure in 0.1~8MPa, preferably 4~8MPa of Hydrogen Vapor Pressure, catalyst quality is 1~
3g, the flow velocity of saturated ester are 0.001~3ml/min, and preferable flow rate is 0.01~0.1ml/min, hydrogen flow rate is 60~
200ml/min, preferable flow rate are 150~200ml/min.
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| CN111302891A (en) * | 2020-04-01 | 2020-06-19 | 华东师范大学 | Method for preparing gasoline and antifreeze from PET plastic |
| CN115073253A (en) * | 2021-03-15 | 2022-09-20 | 中国科学院大连化学物理研究所 | Method for synthesizing dicycloalkane by polycarbonate plastic in one step |
| CN116444343A (en) * | 2023-04-11 | 2023-07-18 | 浙江大学 | Method for preparing 1, 4-cyclohexanedimethanol from waste polyester |
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