CN103252226A - Catalyst for waste plastic microwave pyrolysis and preparation method thereof - Google Patents
Catalyst for waste plastic microwave pyrolysis and preparation method thereof Download PDFInfo
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- CN103252226A CN103252226A CN2013101711932A CN201310171193A CN103252226A CN 103252226 A CN103252226 A CN 103252226A CN 2013101711932 A CN2013101711932 A CN 2013101711932A CN 201310171193 A CN201310171193 A CN 201310171193A CN 103252226 A CN103252226 A CN 103252226A
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Abstract
The invention discloses a catalyst for waste plastic microwave pyrolysis and a preparation method thereof. The catalyst comprises the following components by mass percent: 50.0-90.0% of a microwave absorption component, 9.0-49.9% of a catalytic cracking component, and 0.1-1.0% of a coking inhibiting component. The invention also discloses the preparation method of the catalyst. Compared with the prior art, the catalyst has the advantages that firstly, the catalyst has multiple functions, can effectively convert the microwave electromagnetic energy into heat, provides necessary energy for waste plastic pyrolysis and catalytic cracking, and can reach high equilibrium temperature in action; secondly, the yield of liquid pyrolysis oil is high, no coke is generated in the pyrolysis or the coke is loose and is easy to clear away; and thirdly, the preparation method of the catalyst is simple and is applicable to industrial production.
Description
Technical field
The present invention relates to the catalyst in a kind of environmental protection field, relate in particular to a kind of Catalysts and its preparation method for the waste plastic microwave cracking.
Background technology
Along with the flourish and large-scale use of plastics industry, waste or used plastics goods and plastic garbage bring serious social concern---energy waste and contaminated environment.Mainly contain following several from the chemical composition of waste plastics: polyethylene (comprising low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), high density polyethylene (HDPE) (HDPE)), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), PETG (PET), these several waste plastics account for more than 70% of all kinds waste plastics.
The traditional treatment method of waste plastics is to adopt the method for burning or landfill to handle, and this can produce serious secondary pollution undoubtedly.Waste plastics is a family macromolecule long chain hydrocarbon, the thermal decomposition of plastics is typical breakdown types at random, under the catalyst-free situation, it is fractured into hydrocarbon free radical earlier, the hydrocarbon of regeneration some, wherein contain a large amount of wax shape products, its product is based on alkene, and the molecular weight distribution of pyrolysis product is wideer.These products can change into the high-value product with various uses through further processing to handle.
Yet the required reaction temperature of pyrolysis method is higher, and the reaction time is long, and also very strict to the requirement of hardware facilities such as equipment, resulting fuel oil yield and octane number are all lower.Because the catalytic cracking reaction temperature is low, the added value of product height, thereby become the emphasis of domestic and international research.For example, Chinese patent CN101695666A (Yang Rong equality, the catalyst that a kind of scrap rubber, waste plastic oil-refining cracking are used) catalyst that a kind of scrap rubber, waste plastic oil-refining cracking are used is disclosed, this catalyst is by weight with 30～60 parts of tricalcium silicates, 15～37 parts of dicalcium silicates, 7～15 parts of tricalcium aluminates, 10～18 parts of tetra calcium aluminoferrites, 20～30 parts in calcium oxide, 10～15 parts in calcium carbonate, 2～5 parts of sodium oxide molybdenas, 1～3 part of potassium oxide, mixes to be crushed to 200 orders by ball mill and to mix.Catalyst consumption is 1～10% of scrap rubber, waste plastics.Chinese patent CN1462790A (Wang Yuzhong etc., be used for cracking waste plastics to produce the catalyst of fuel oil) provide for cracking waste plastics to produce the catalyst of fuel oil, this catalyst is a kind of ZSM-5 zeolite molecular sieve of metal oxide modified, catalyst is active high, be used for not only reaction time weak point of cracking waste plastics, and cracking temperature is low, can greatly reduce production cost; The comprehensive yield height of the fuel oil of producing is all more than 80%.US Patent No. 7862691B2 (Kitamura et al, Decomposition method of waste plastics and organics) discloses a kind of for the method for decomposing waste plastics and organic waste.The catalyst that adopts is titanium dioxide granule, and the specific area of described catalyst is 33～65 m
2/ g, particle diameter are 3.5 orders (5.6 mm).When reaction temperature was lower than 300 ℃, titanium dioxide was without any catalytic effect, and waste plastics only melts and do not decompose.When temperature surpassed 350 ℃, waste plastics slightly decomposed, 420～560 ℃ of suitable range of reaction temperature.
Though existing waste plastics catalytic cracking catalyst is various in style, also obtained corresponding catalytic pyrolysis effect separately, yet from inventor's result of use, still there is following problem in above-mentioned catalyst: 1) activity of such catalysts is lower, reaction time is long, usually more than several hrs, reaction temperature is usually more than 500 ℃, the energy consumption height of cracking process.2) function singleness of catalyst only has the function of catalytic pyrolysis, and when handling the waste plastics of complicated component, the quality of cracked oil is lower.3) cinder of cracking waste plastics generation covers the surface of reactor and catalyst, has reduced activity of such catalysts, and has been not easy to remove cinder.
In recent years on the research basis of traditional pyrolysis, propose and developed the microwave cracking technology in conjunction with microwave heating technique.Microwave be frequency between the frequency electromagnetic waves of 30 MHz～300 GHz, its can integral body penetrate organic matter, and energy is reached rapidly in the functional group of reactant.Heating using microwave is the volume heating that is caused by dielectric loss in the electromagnetic field, and under electromagnetic field effect, molecular motion becomes orderly dither by original rambling state, and molecular kinetic energy is transformed into heat energy, reaches the purpose of even heating.In certain microwave field, the ability of material absorption microwave is relevant with its dielectric properties and electromagnetic property, and the polar molecule that dielectric constant is bigger and microwave have stronger coupling, microwave energy can be converted into spread heat in material.
Based on the characteristics of above heating using microwave, the researcher is applied to organic pyrolysis art with heating using microwave both at home and abroad, has shown the superiority of microwave-heating, is a kind of fine selection of alternative conventional pyrolysis.For example, Chinese patent CN101972622A (Zhang Li know etc., a kind of blue-green algae microwave improvement method based on carbon-supported catalysts) provides a kind of blue-green algae microwave improvement method based on carbon-supported catalysts, can realize efficiently killing blue-green algae in the extremely short time.Chinese patent CN100999677A (Wang Jun etc., the method of preparing rich furol biological oil by biomass microwave catalytic pyrolysis) with ferric sulfate is catalyst, be the microwave absorbing medium with carborundum, be that heating source carries out the bio oil that biomass cracking obtains to be rich in furfural with the microwave source, the cracking reaction time is short, and 5～15 min can finish reaction.US Patent No. 5268548A (Kumar, Microwave assisted paint stripping) has introduced a kind of method that adopts microwave cracking paint or paint coatings, and the microwave absorbing material that uses is MnO
2, NiO, WO
3, CoO, C, FeTiO
3, can in a few minutes, coating be heated to more than 1200 ℃.
Yet, the substance classes difference, there is very big difference in the dielectric constant of material, and the heating using microwave of material depends on its dielectric constant, it has determined whether this material can produce heat under the effect of microwave.The dielectric constant of plastics is very little, absorb the microwave ability a little less than, thereby need very long exposure time just can cause pyrolysis, even pyrolysis can not take place in irradiation for a long time yet.If will realize the microwave-heating of waste plastics, need to add a certain amount of " microwave absorption ", material is rapidly heated and pyrolysis takes place.
Recently, the microwave cracking technology has also obtained good application in the cracking of waste plastics.For example, international monopoly WO2012097448A1(Doucent et al, Catalyst for distributed bach microwave pyrolysis, system and process thereof) introduced a kind of catalyst that can excite microwave cracking.The catalyst that adopts is the graphite of carbon content 80～90%, and this catalyst is mainly for the treatment of family's discarded object, for example Fei Qi food, garden discarded object, packing case, disregard message paper, clothing, plastics etc.The volume of discarded object can be reduced more than 90%, reduce by 60～70% discarded object transportation, collection, disposal cost.Pyrolysis product comprises gas, liquid and solid residue, and under the condition of using catalyst, the ratio of gas is higher in the pyrolysis product.International monopoly WO2012110990A1 (Frediani et al, Production of hydrocarbons from copyrolysis of plastic and tyre material with microwave heating) discloses the method for a kind of employing microwave degradation waste plastics (PE, PP, PS, PET, PVC and composition thereof) and waste tire or tire pyrolysis residue.The sulfur content of cracked oil is less than 1%, and the cut that its mid-boiling point is 20～250 ℃ surpasses 50%.Because plastics have very little dielectric constant and loss factor, being difficult to absorb microwave is heated, what therefore play the absorption microwave action is waste tire or tire pyrolysis residue, the mass ratio of waste plastics and damaged tire is 1:1.5～1:4.0, and the mass ratio of waste plastics and tire pyrolysis residue is 1:1～1:2.0.
Yet, the inventor finds that still there is following problem in above-mentioned catalyst in the process that adopts microwave cracking technical finesse waste plastics: the 1) function singleness of catalyst only has the function of fast pyrolysis, the productive rate of cracked oil is less, and microwave cracking is than the more gas of conventional method output.2) contain unsaturated compounds such as more alkene, alkadienes, aromatic hydrocarbons in the cracked gas, these unsaturated compounds are extremely unstable, and especially Diels – Alder cyclization and polymerisation very easily take place after being heated alkadienes, molecule is grown up gradually, form macromolecule polyalcohol.The little coke powder particle that forms in the cracking process has very strong adsorptivity, easily and the organic macromolecule compound that forms in the polymerisation be bonded together, burnt dirty particle is grown up gradually, be deposited on the surface of catalyst and reactor, reduced reaction rate, and be difficult to remove.
Based on above analysis, the catalyst that reasonably is used for the waste plastics microwave cracking should satisfy following three functions simultaneously: 1) absorb the function of microwave, make the electromagnetic energy of microwave convert heat energy to, waste plastics is rapidly heated and pyrolysis takes place; 2) function of catalytic pyrolysis can reduce the activation energy of reaction, and C-C key chain-breaking reaction takes place under lower reaction temperature on demand, accelerates the carrying out of cracking waste plastics reaction, improves reaction efficiency; 3) function of inhibition coking changes the radical reaction course, and inhibitory reaction coking, and the physical aspect of change coking make it to become loose cinder, are easy to remove.
Summary of the invention
Shortcomings such as function singleness, the oil product yield that exists at the waste plastics microwave cracking catalyst of prior art is low, easy coking the purpose of this invention is to provide a kind of a kind of catalyst for the waste plastics microwave cracking that absorbs microwave, catalytic pyrolysis, these three kinds of functions of inhibition coking that has simultaneously.
A further object of the present invention provides above-mentioned for waste plastics microwave cracking Preparation of catalysts method.
The object of the invention is achieved through the following technical solutions: a kind of catalyst for the waste plastics microwave cracking, comprise catalytic pyrolysis component and microwave absorbent components, and also comprise the coking constituents for suppressing, each component is by mass parts:
The microwave absorbent components is 50.0～90.0%
The catalytic pyrolysis component is 9.0～49.9%
The coking constituents for suppressing is 0.1～1.0%,
Wherein, described microwave absorbent components is that particle diameter is any or its combination in 10～800 purpose carbon compounds, silicon-containing compound, iron containing compounds, the high molecular polymer;
Described catalytic pyrolysis component is that particle diameter is 10～800 purpose γ-Al
2O
3, any or its combination in the amorphous silicic aluminium, flyash, zeolite molecular sieve, natural ore deposit soil, solid acid;
Described coking constituents for suppressing is any or its combination in alkali metal salt, phosphorus-containing compound, boron-containing compound, magnesium sulfate, diethyl polysiloxanes, the p-tert-butyl catechol.
On the such scheme basis, described carbon compound is any or its combination in active carbon, coke, coal, carbon fiber, CNT, graphite, pitch, the Graphene; Described silicon-containing compound is any or its combination in monocrystalline silicon, the silicon nitride; Described iron containing compounds is any or its combination in iron oxide, carbonyl iron, iron sulfide, the ferrous titanate; Described high molecular polymer is any or its combination in polyacetylene, polypyrrole, the polyaniline.
On the such scheme basis, described zeolite molecular sieve is any or its combination in HZSM-5, H β, HY, SAPO-34, SBA-15, MCM-41, modenite, the clinoptilolite; Described natural ore deposit soil is any or its combination in atlapulgite, attapulgite, kaolin, bentonite, imvite, the mica soil; Described solid acid is metatitanic acid, SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2In any or its combination.
On the such scheme basis, described alkali metal salt is any or its combination in potassium acetate, sodium acetate, potash, potassium dihydrogen phosphate, the vulcanized sodium; Described phosphorus-containing compound is any or its combination in phosphoric acid, triethyl phosphate, the triphenyl phosphate; Described boron-containing compound is any or its combination in boric acid, the Boratex.
The invention provides and a kind ofly take by weighing, prepare microwave absorbent components, catalytic pyrolysis component and coking constituents for suppressing at above-mentioned respectively for waste plastics microwave cracking Preparation of catalysts method, may further comprise the steps:
(1) microwave absorbent components and catalytic pyrolysis component are joined in the mixer, continue to stir 1 hour (h), the homogeneous mixture that obtains microwave absorbent components and catalytic pyrolysis component is material 1;
(2) the coking constituents for suppressing is dissolved in 10～100 times the solvent, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 100 ℃ of following vacuum drying 2 hours, remove obtain behind the solvent described for waste plastics microwave cracking catalyst.
On the such scheme basis, described solvent is any or its combination in water, alcohols, petroleum distillate, coal tar, the shale oil.
On the such scheme basis, described alcohols is any or its combination in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the butanols; Described petroleum distillate is any or its combination in naphtha, gasoline, kerosene, diesel oil, the wax oil.
The invention provides a kind of using method for waste plastics microwave cracking catalyst: take by weighing described catalyst and waste plastics, carry out the microwave cracking reaction after mixing, described catalyst consumption is 1～10% of waste plastics quality, and the frequency that the microwave cracking reaction is adopted is 915 MHz or 2450 MHz.
Microwave cracking reaction described in the present invention can be carried out in microwave reactor, and catalyst and waste plastics are put into quartz bottle and abundant the mixing, for guaranteeing the inert environments in the quartz bottle, the enough nitrogen of necessary feeding earlier before reaction.In the course of reaction fixedly the power of microwave be 700 W, adopt the equilibrium temperature that sample can reach in the infrared optics thermometer determination experiment process.Pyrolysis product obtains the liquid cracked oil through condensation separation, calculates gas recovery ratio (gas recovery ratio=100% – liquid Shou Shuai – solid yield) according to liquid yield and solid yield.
On the such scheme basis, described waste plastics is any or its combination in waste polyethylene (PE), waste polypropylene (PP), deposed polystyrene (PS), useless PETG (PET), the waste polyvinyl chloride (PVC).
Compared with the prior art, advantage of the present invention is: one, catalyst have multiple function, can be effectively convert the electromagnetic energy of microwave to heat energy, provide waste plastics pyrolysis and catalytic pyrolysis necessary energy, the equilibrium temperature height that course of reaction can reach.Its two, loose, the easy-clear of cinder when the yield height of liquid cracked oil, cracking process do not have coking or coking is arranged.Its three, the Preparation of catalysts method is simple, suitability for industrialized production.
Description of drawings
Fig. 1 is that the catalyst of table 1 embodiment 1～20 is formed and the pyrolysis product yield, and wherein, microwave absorption is one pack system;
Fig. 2 is that the catalyst of table 2 embodiment 21～26 is formed and the pyrolysis product yield, and wherein, microwave absorption is the one pack system bi-component;
Fig. 3 is that the catalyst of table 3 comparative example 1～4 is formed and the pyrolysis product yield.
The specific embodiment
The technical characterictic that the invention is further illustrated by the following examples, but be not limited to embodiment.
Preparation of catalysts:
(1) with 50.0 g, 10 purpose active carbons and 49.9 g, 10 purpose γ-Al
2O
3Join in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.1 g potassium acetate is dissolved in the water of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 10.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 315 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 90.0 g, 800 purpose coke and 9.0 g, 800 purpose amorphous silicic aluminium are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 1.0 g sodium acetates are dissolved in the water of 10 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polypropylenes (PP) of 1.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 408 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 80.0 g, 500 purpose coals and 19.5 g, 500 purpose flyash are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.5 g potash is dissolved in the water of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 915 MHz, and the equilibrium temperature that course of reaction can reach is 600 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 80.0 g, 100 purpose carbon fibers and 19.0 g, 100 purpose HZSM-5 are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 1.0 g potassium dihydrogen phosphates are dissolved in the water of 20 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the useless PETG (PET) of 100 g of 2.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 425 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 80.0 g, 200 purpose CNTs and 19.0 g, 200 purpose H β are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 1.0 g vulcanized sodium are dissolved in the water of 20 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyvinyl chlorides (PVC) of 3.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 470 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 6
Preparation of catalysts:
(1) 80.0 g, 200 purpose graphite and 19.0 g, 200 purpose HY are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 1.0 g phosphoric acid are dissolved in the methyl alcohol of 10 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing methyl alcohol, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 552 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 70.0 g, 100 purpose pitches and 29.5 g, 200 purpose SAPO-34 are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.5 g triethyl phosphate is dissolved in the ethanol of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing ethanol, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 8.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 460 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 90.0 g, 200 purpose monocrystalline silicon and 9.8 g, 200 purpose SBA-15 are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.2 g triphenyl phosphate is dissolved in the propyl alcohol of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing propyl alcohol, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 370 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 9
Preparation of catalysts:
(1) 85.0 g, 300 purpose silicon nitrides and 14.5 g, 200 purpose MCM-41 are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.5 g boric acid is dissolved in the water of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polypropylenes (PP) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 381 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 60.0 g, 300 purpose iron oxide and 39.0 g, 300 purpose modenites are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 1.0 g Boratexes are dissolved in the water of 20 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polypropylenes (PP) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 915 MHz, and the equilibrium temperature that course of reaction can reach is 433 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 11
Preparation of catalysts:
(1) 70.0 g, 300 purpose carbonyl irons and 29.0 g, 300 purpose clinoptilolites are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 1.0 g magnesium sulfate are dissolved in the water of 10 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 915 MHz, and the equilibrium temperature that course of reaction can reach is 542 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 80.0 g, 300 purpose iron sulfide and 19.8 g, 300 purpose atlapulgites are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.2 g diethyl polysiloxanes is dissolved in the isopropyl alcohol of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing isopropyl alcohol, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 503 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 13
Preparation of catalysts:
(1) 90.0 g, 200 purpose ferrous titanates and 9.8 g, 200 purpose attapulgites are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.2 g diethyl polysiloxanes is dissolved in the butanols of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing butanols, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 422 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 14
Preparation of catalysts:
(1) 50.0 g, 200 purpose polyacetylene and 49.9 g, 200 purpose kaolin are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.1 g p-tert-butyl catechol is dissolved in the naphtha of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing naphtha, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 7.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 345 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) 60.0 g, 200 purpose polypyrroles and 39.9 g, 200 purpose bentonites are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.1 g p-tert-butyl catechol is dissolved in the gasoline of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing gasoline, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 7.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 398 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 16
Preparation of catalysts:
(1) 70.0 g, 200 purpose polyanilines and 29.9 g, 200 purpose imvites are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.1 g p-tert-butyl catechol is dissolved in the kerosene of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing kerosene, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 7.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 424 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 17
Preparation of catalysts:
(1) 80.0 g, 200 purpose Graphenes and 19.9 g, 200 purpose mica soil are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.1 g p-tert-butyl catechol is dissolved in the diesel oil of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing diesel oil, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 4.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 516 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 18
Preparation of catalysts:
(1) 85.0 g, 200 purpose coke and 14.5 g, 200 purpose metatitanic acids are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.5 g triphenyl phosphate is dissolved in the wax oil of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing wax oil, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polypropylenes (PP) of 4.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 378 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 19
Preparation of catalysts:
(1) with 85.0 g, 200 purpose coals and 14.5 g, 200 purpose SO
4 2-/ TiO
2Join in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.5 g triphenyl phosphate is dissolved in the coal tar of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing coal tar, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polypropylenes (PP) of 4.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 438 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Preparation of catalysts:
(1) with 85.0 g, 200 purpose graphite and 14.5 g, 200 purpose SO
4 2-/ ZrO
2Join in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.5 g triphenyl phosphate is dissolved in the shale oil of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing shale oil, the composition of catalyst sees Table 1.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polypropylenes (PP) of 4.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 527 ℃, and the yield of microwave cracking product and coking situation see Table 1.
Embodiment 21
Preparation of catalysts:
(1) 70.0 g, 200 purpose graphite, 10.0 g, 200 purpose coals and 10.0 g, 200 purpose HY, 9.5 g, 200 purpose HZSM-5 are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.3 g potassium acetate, 0.2 g potassium dihydrogen phosphate are dissolved in the water of 10 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 2.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g deposed polystyrenes (PS) of 5.0 g present embodiments, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, and the equilibrium temperature that course of reaction can reach is 544 ℃, and the yield of microwave cracking product and coking situation see Table 2.
Embodiment 22
Preparation of catalysts:
(1) 70.0 g, 200 purpose monocrystalline silicon, 10.0 g, 200 purpose silicon nitrides and 10.0 g, 200 purpose atlapulgites, 9.5 g, 200 purpose kaolin are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.3 g phosphoric acid, 0.2 g triethyl phosphate are dissolved in the propyl alcohol of ethanol, 5 g of 10 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing ethanol and propyl alcohol, the composition of catalyst sees Table 2.
The microwave cracking reaction:
Take by weighing the catalyst of 5.0 g present embodiments and 50 g waste polyethylenes (PE), 50 g deposed polystyrenes (PS), carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 375 ℃, and the yield of microwave cracking product and coking situation see Table 2.
Embodiment 23
Preparation of catalysts:
(1) with 80.0 g, 200 purpose iron oxide, 5.0 g, 200 purpose iron sulfide and 10.0 g, 200 purpose metatitanic acids, 4.8 g, 200 purpose SO
4 2-/ ZrO
2Join in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.2 g triethyl phosphate is dissolved in the diesel oil of gasoline, 5 g of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing gasoline and diesel oil, the composition of catalyst sees Table 2.
The microwave cracking reaction:
Take by weighing the catalyst of 5.0 g present embodiments and 50 g waste polyethylenes (PE), 50 g deposed polystyrenes (PS), carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 446 ℃, and the yield of microwave cracking product and coking situation see Table 2.
Embodiment 24
Preparation of catalysts:
(1) with 80.0 g, 200 purpose polyacetylene, 5.0 g, 200 purpose polyanilines and 10.0 g, 200 purpose metatitanic acids, 4.5 g, 200 purpose SO
4 2-/ ZrO
2Join in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.2 g boric acid, 0.3 g Boratex are dissolved in the 10 g water, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 2.
The microwave cracking reaction:
Take by weighing the catalyst of 5.0 g present embodiments and 50 g waste polyethylenes (PE), 50 g deposed polystyrenes (PS), carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 417 ℃, and the yield of microwave cracking product and coking situation see Table 2.
Embodiment 25
Preparation of catalysts:
(1) 75.0 g, 200 purpose graphite, 5.0 g, 200 purpose iron oxide and 15.0 g, 200 purpose atlapulgites, 4.5 g, 200 purpose HY are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.3 g potassium acetate, 0.2 g magnesium sulfate are dissolved in the ethanol of water, 2 g of 10 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water and ethanol, the composition of catalyst sees Table 2.
The microwave cracking reaction:
Take by weighing the catalyst of 5.0 g present embodiments and 50 g waste polyethylenes (PE), 30 g deposed polystyrenes (PS), 20 g waste polyvinyl chlorides (PVC), carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 578 ℃, and the yield of microwave cracking product and coking situation see Table 2.
Embodiment 26
Preparation of catalysts:
(1) 75.0 g, 200 purpose pitches, 5.0 g, 200 purpose iron sulfide and 15.0 g, 200 purpose mica soil, 4.5 g, 200 purpose metatitanic acids are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.3 g phosphoric acid, 0.2 g boric acid are dissolved in the water of 5 g, obtain solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing water, the composition of catalyst sees Table 2.
The microwave cracking reaction:
Take by weighing the catalyst of 5.0 g present embodiments and 50 g waste polyethylenes (PE), 30 g deposed polystyrenes (PS), 20 g waste polyvinyl chlorides (PVC), carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 527 ℃, and the yield of microwave cracking product and coking situation see Table 2.
Comparative example 1
Compare with embodiment 8, do not contain the microwave absorbent components in the microwave cracking catalyst, but contain catalytic pyrolysis component and coking constituents for suppressing.
Preparation of catalysts:
(1) 99.8 g, 200 purpose SBA-15 is joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.2 g triphenyl phosphate is dissolved in the propyl alcohol of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing propyl alcohol, the composition of catalyst sees Table 3.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 5.0 these comparative examples of g, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 268 ℃, the yield liquid of microwave cracking product is 20.4%, far below 78.3% of embodiment 8, and coking is arranged, the yield of microwave cracking product and coking situation see Table 3.
Comparative example 2
Compare with embodiment 8, do not contain the catalytic pyrolysis component in the microwave cracking catalyst, but contain microwave absorbent components and coking constituents for suppressing.
Preparation of catalysts:
(1) 99.8 g, 200 purpose monocrystalline silicon is joined in the mixer, continue to stir 1 h, obtain material 1;
(2) 0.2 g triphenyl phosphate is dissolved in the propyl alcohol of 10 g, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 at 100 ℃ of following vacuum drying 2 h, obtain the microwave cracking catalyst after removing propyl alcohol, the composition of catalyst sees Table 3.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 5.0 these comparative examples of g, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 418 ℃, the yield liquid of microwave cracking product is 73.2%, be lower than 78.3% of embodiment 8, the yield of microwave cracking product and coking situation see Table 3.
Comparative example 3
Compare with embodiment 8, do not contain the coking constituents for suppressing in the microwave cracking catalyst, but contain microwave absorbent components and catalytic pyrolysis component.
Preparation of catalysts:
90.0 g, 200 purpose monocrystalline silicon and 10 g, 200 purpose SBA-15 are joined in the mixer, continue to stir 1 h, obtain the microwave cracking catalyst, the composition of catalyst sees Table 3.
The microwave cracking reaction:
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 5.0 these comparative examples of g, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 372 ℃, the coking that removes in distress, the yield of microwave cracking product and coking situation see Table 3.
Comparative example 4
This comparative example adopts be that embodiment 1 provides among the US Patent No. 6184427B1 (Klepfer et al, Process and reactor for microwave cracking of plastic materials) be deposited on 15%NiO/ activated-carbon catalyst on the active carbon.
Take by weighing catalyst and the 100 g waste polyethylenes (PE) of 5.0 these comparative examples of g, carry out the microwave cracking reaction after mixing, the frequency of microwave is 2450 MHz, the equilibrium temperature that course of reaction can reach is 343 ℃, the coking that removes in distress, the yield liquid of microwave cracking product is 58.2%, is lower than 78.3% of embodiment 8, and the yield of microwave cracking product and coking situation see Table 3.
Claims (9)
1. a catalyst that is used for the waste plastics microwave cracking comprises catalytic pyrolysis component and microwave absorbent components, it is characterized in that: also comprise the coking constituents for suppressing, each component is by mass parts:
The microwave absorbent components is 50.0～90.0%
The catalytic pyrolysis component is 9.0～49.9%
The coking constituents for suppressing is 0.1～1.0%,
Wherein, described microwave absorbent components is that particle diameter is any or its combination in 10～800 purpose carbon compounds, silicon-containing compound, iron containing compounds, the high molecular polymer;
Described catalytic pyrolysis component is that particle diameter is 10～800 purpose γ-Al
2O
3, any or its combination in the amorphous silicic aluminium, flyash, zeolite molecular sieve, natural ore deposit soil, solid acid;
Described coking constituents for suppressing is any or its combination in alkali metal salt, phosphorus-containing compound, boron-containing compound, magnesium sulfate, diethyl polysiloxanes, the p-tert-butyl catechol.
2. the catalyst for the waste plastics microwave cracking according to claim 1 is characterized in that: described carbon compound is any or its combination in active carbon, coke, coal, carbon fiber, CNT, graphite, pitch, the Graphene; Described silicon-containing compound is any or its combination in monocrystalline silicon, the silicon nitride; Described iron containing compounds is any or its combination in iron oxide, carbonyl iron, iron sulfide, the ferrous titanate; Described high molecular polymer is any or its combination in polyacetylene, polypyrrole, the polyaniline.
3. the catalyst for the waste plastics microwave cracking according to claim 1 is characterized in that: described zeolite molecular sieve is any or its combination in HZSM-5, H β, HY, SAPO-34, SBA-15, MCM-41, modenite, the clinoptilolite; Described natural ore deposit soil is any or its combination in atlapulgite, attapulgite, kaolin, bentonite, imvite, the mica soil; Described solid acid is metatitanic acid, SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2In any or its combination.
4. the catalyst for the waste plastics microwave cracking according to claim 1 is characterized in that: described alkali metal salt is any or its combination in potassium acetate, sodium acetate, potash, potassium dihydrogen phosphate, the vulcanized sodium; Described phosphorus-containing compound is any or its combination in phosphoric acid, triethyl phosphate, the triphenyl phosphate; Described boron-containing compound is any or its combination in boric acid, the Boratex.
5. one kind is characterized in that for waste plastics microwave cracking Preparation of catalysts method according to each of claim 1 to 4 is described, takes by weighing, prepares microwave absorbent components, catalytic pyrolysis component and coking constituents for suppressing respectively, may further comprise the steps:
(1) microwave absorbent components and catalytic pyrolysis component are joined in the mixer, continue to stir 1 h, obtain material 1;
(2) the coking constituents for suppressing is dissolved in 10～100 times the solvent, obtains solution 1;
(3) in whipping process, the solution 1 of step (2) gained is sprayed onto on the material 1 of step (1) gained, obtain material 2;
(4) with material 2 100 ℃ of following vacuum drying 2 hours, remove obtain behind the solvent described for waste plastics microwave cracking catalyst.
6. according to claim 5 for waste plastics microwave cracking Preparation of catalysts method, it is characterized in that: described solvent is any or its combination in water, alcohols, petroleum distillate, coal tar, the shale oil.
7. according to claim 6 for waste plastics microwave cracking Preparation of catalysts method, it is characterized in that: described alcohols is any or its combination in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the butanols; Described petroleum distillate is any or its combination in naphtha, gasoline, kerosene, diesel oil, the wax oil.
8. according to each described using method for waste plastics microwave cracking catalyst of claim 1 to 4, it is characterized in that: take by weighing catalyst and waste plastics, carry out the microwave cracking reaction after mixing, described catalyst consumption is 1～10% of waste plastics quality, and the frequency that the microwave cracking reaction is adopted is 915 MHz or 2450 MHz.
9. the using method for waste plastics microwave cracking catalyst according to claim 8 is characterized in that: described waste plastics is any or its combination in waste polyethylene, waste polypropylene, deposed polystyrene, useless PETG, the waste polyvinyl chloride.
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