CN101891581B - Method for recovering styrene and other aromatic hydrocarbon raw materials by catalyzing and cracking waste polystyrene - Google Patents
Method for recovering styrene and other aromatic hydrocarbon raw materials by catalyzing and cracking waste polystyrene Download PDFInfo
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- CN101891581B CN101891581B CN201010206721XA CN201010206721A CN101891581B CN 101891581 B CN101891581 B CN 101891581B CN 201010206721X A CN201010206721X A CN 201010206721XA CN 201010206721 A CN201010206721 A CN 201010206721A CN 101891581 B CN101891581 B CN 101891581B
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 33
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 21
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- 238000005336 cracking Methods 0.000 title abstract description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title abstract description 7
- 239000002699 waste material Substances 0.000 title abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 5
- 230000007017 scission Effects 0.000 claims description 5
- 238000010504 bond cleavage reaction Methods 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 239000012263 liquid product Substances 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 230000009466 transformation Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a new method for catalyzing and cracking waste polystyrene (PS) to generate aromatic hydrocarbon raw materials, such as styrene and the like, so as to realize chemical recycling of the polystyrene. The method is characterized by adopting a mesoporous molecular sieve MxO/MCM-41 carrying alkali metals and/or alkaline-earth metals as a catalyst (wherein M is an alkali metal and an alkaline-earth metal, such as Li, Na, K, Mg, Ca, Ba and the like, or a compound thereof, and x is 1 or 2) and comprising the steps of: carrying out cracking reaction at 300-450 DEG C in the presence of normal pressures, or pressure reduction or nitrogen introduction; and obtaining aromatic hydrocarbon compounds, such as toluene, ethylbenzene, styrene and the like, by operations of rectification and the like after reaction. The catalyst can be recycled directly without any processing. The cracking rate of the polystyrene is greater than or equal to 98%, the yield of a liquid product is greater than or equal to 95%, and the content of styrene in the liquid product is above 80%. Compared with the prior art, the method has the characteristics that the yield of liquid and the selectivity of styrene are higher, the reaction temperature is mild, and the recycling property of the catalyst is good.
Description
Technical field
The present invention relates to a kind ofly take basic metal and/or alkali-earth metal modified MCM-41 mesoporous molecular sieve as catalyzer, the catalytic pyrolysis deposed polystyrene generates the novel method that styrene and other aromatic hydrocarbon raw materials realizes that its chemical cycle reclaims.
Background technology
Polystyrene refers to the polymkeric substance that made through Raolical polymerizable by styrene monomer, is called for short PS.It is a kind of thermoplastics, is widely used as antidetonation, insulation and wrapping material etc.Along with developing rapidly of the industry such as household electrical appliances, instrument, electronics, food, the consumption of polystyrene plastic increases rapidly, and its turnout and consumption rise year by year, and a large amount of uses of PS have simultaneously also caused the generation of a large amount of useless PS.Being difficult to degraded voluntarily due to PS under physical environment, thereby can causing serious environmental pollution, is also the huge wasting of resources simultaneously.Therefore, the recycle of useless PS is subject to people's attention day by day in recent years.
At present, the method for useless PS closed matereial cycle is mainly contained two classes, a class is Physical, namely mould by melting or the low product of preparation added value is moulded in granulation again, but the secondary use properties of useless PS is relatively poor again, thereby has limited the application of this method.Another kind of is chemical method, namely reclaims the chemical composition of deposed polystyrene by chemical process, makes it to become monomer or fuel.The method mainly contains pyrolysis method and catalystic pyrolysis at present.(Fuel Process Technology, 2000,63 (1): 45-55) heat scission reaction at 600 ℃ of lower p-poly-phenyl ethene is studied, and can obtain the vinylbenzene yield of 78.7wt% such as Liu etc.The shortcoming of the method be need to be higher temperature, cause the power consumption larger.
The catalyzer that catalytic pyrolysis process is commonly used mainly contains acidic molecular sieve and metal oxide etc.Traditional molecular sieve catalyst and metal oxide etc. are because its aperture is less, and larger polystyrene molecule is difficult for entering its internal surface, and majority surface reaction outside not only affects its effective active, and makes product liquid and styrene monomer elective reduction.In addition, the repetition reuse poor-performing of catalyzer.Metal oxides such as CN1105351A employing zinc oxide, ferric oxide and a small amount of rare-earth oxide are cracking catalyst PS, and cinnamic yield is 35-60%.The catalyst cracking PS that the Y zeolite of the special modification of CN1106371A use and the aluminum oxide of high-specific surface area process under special conditions, the vinylbenzene yield is below 60%.The metal oxides such as US 5072068 employing oxidations are catalyzer, and add a large amount of alloy additions such as particulate state lead zinc to prevent coking at reactor bottom, but this method needs the high temperature of 450 ℃-500 ℃, and easily cause Lead contamination.In addition, do not mention the repetition reuse result of catalyzer yet.Therefore adopt new catalyst to improve existing technique drawback, realize that recovering styrene and other aromatic hydrocarbon raw materials by catalyzing and cracking waste polystyrene is significant.
Summary of the invention
The present invention proposes a kind of catalytic pyrolysis deposed polystyrene and reclaim the novel method that styrene and other aromatic hydrocarbon raw materials realizes that its chemical cycle reclaims.It is catalyzer that the method adopts a kind of basic metal and/or alkali-earth metal modified MCM-41 mesoporous molecular sieve of larger aperture, deposed polystyrene is carried out catalytic cracking reaction, relax reaction conditions on the one hand, improved liquid product yield and selectivity of styrene, can realize on the other hand the recycling of catalyzer.
The purpose of this invention is to provide the novel method that a kind of catalytic pyrolysis deposed polystyrene reclaims the aroamtic hydrocarbon raw materials such as styrene monomer, overcome that traditional method cracking deposed polystyrene exists or temperature of reaction is too high or liquid product yield and selectivity of styrene is low or catalyzer repeats the shortcomings such as reuse poor performance.
The present invention is by these problems of following solution: adopting basic metal and/or alkali-earth metal modified MCM-41 mesoporous molecular sieve is catalyzer, the catalyzer and the deposed polystyrene that mix are by a certain percentage added in reactor, in normal pressure or decompression or pass under condition of nitrogen gas, carry out at a certain temperature scission reaction.After reaction finished, the gained product liquid obtained styrene monomer through operations such as rectifying.Catalyzer is without any processing direct reuse.Polystyrene cleavage rate 〉=98%, liquid product yield 〉=95%, in product liquid, styrene content is more than 80%.
Catalyzer of the present invention is the mesoporous molecular sieve MxO/MCM-41 of carrying alkali metal and/or alkaline-earth metal, and wherein M is alkali and alkaline earth metal ions or its mixtures such as Li, Na, K, Mg, Ca, Ba; X=1 or 2, the most frequently used is alkali and alkaline earth metal ions or its mixtures such as K, Mg, Ca, Ba.The preparation of catalyzer can be adopted blending method or load method, concrete grammar following (with the example that is prepared as of BaO-MCM-41):
Blending method prepares BaO-MCM-41
Adopt hydrothermal synthesis method to prepare the BaO-MCM-41 catalyzer, the proportioning raw materials of using is: n (BaCl
2): n (SiO
2): n (Na
2O): n (CTAMBr/ cetyl trimethylammonium bromide): n (H
2O)=1/30-80: 1: 0.67: 0.2: 122.Synthesis step is as follows:
1. weigh respectively CTAMBr, the Na of certain mass by above each atom ratio
2SiO
39H
2The silica gel of O, massfraction 30%, BaCl
2, deionized water.
2. use respectively deionized water dissolving CTAMBr, Na
2SiO
39H
2O and BaCl
2
3. with part Na
2SiO
3The aqueous solution adds in the CTAMBr aqueous solution to get A; Another part Na
2SiO
3The aqueous solution adds in silica gel, can produce the jelly shape and stick with paste, and immediately it is added in A, stirs 1h under normal temperature.
4. with BaCl
2The aqueous solution adds in A, stirs 0.5h under normal temperature, obtains initial gel mixture.
5. under agitation, the HCl accent pH value to 8.5 with 1mol/l stirs 1h under normal temperature.
6. mixture is moved in the teflon-lined stainless steel reactor, the sealing, in loft drier in 100 ℃ of crystallization 24h.
7. after crystallization finishes, the crystalline solid product is separated with mother liquor, with about 1.5L deionization, that the washing of crystalline solid product is extremely neutral.
8. will wash extremely neutral crystalline solid product and put into loft drier, in 70 ℃ of dry 12h.
9. dried product is put into retort furnace, make the BaO-MCM-41 catalyzer in 550 ℃ of roasting 8h.Load method prepares BaO-MCM-41
At first adopt hydrothermal synthesis method to prepare MCM-41, the proportioning raw materials of using is: n (SiO
2): n (Na
2O): n (CTAMBr): n (H
2O)=1: 0.67: 0.2: 122.Synthesis step is as follows:
1. weigh respectively CTAMBr, the Na of certain mass by above atom ratio
2SiO
39H
2The silica gel of O, massfraction 30%, deionized water.
2. use respectively deionized water dissolving CTAMBr and Na
2SiO
39H
2O。
3. with part Na
2SiO
3The aqueous solution adds in the CTAMBr aqueous solution to get B; Another part Na
2SiO
3The aqueous solution adds in silica gel, can produce the jelly shape and stick with paste, and immediately it is added in B.Stir 1h under normal temperature, obtain initial gel mixture.
4. under agitation, the HCl accent pH value to 8.5 with 1mol/l stirs 1h under normal temperature.
5. mixture is moved in the teflon-lined stainless steel reactor, the sealing, in loft drier in 100 ℃ of crystallization 24h.
6. after crystallization finishes, the crystalline solid product is separated with mother liquor, with about 1.5L deionization, that the washing of crystalline solid product is extremely neutral.
7. will wash extremely neutral crystalline solid product and put into loft drier, in 70 ℃ of dry 12h.
8. dried product is put into retort furnace, make MCM-41 in 550 ℃ of roasting 8h.Then, adopt load method to prepare the BaO-MCM-41 catalyzer, concrete steps are as follows:
1. prepare the BaCl of the different volumetric molar concentrations such as 0.05mol/l, 0.10mol/l, 0.20mol/l
2The aqueous solution.
2. use respectively the BaCl of the different volumetric molar concentrations such as 15mL 0.05mol/l, 0.10mol/l, 0.20mol/l
2Aqueous solution soaking 1gMCM-41 mesoporous molecular sieve, suction filtration after stirring 50min.
3. with the product after suction filtration in loft drier in 70 ℃ of dry 12h.
4. with dried product in retort furnace in 600 ℃ of roasting 3h, make the BaO-MCM-41 catalyzer of different loads amount.
The same BaO-MCM-41 of the preparation method of other catalyzer.
The described temperature of reaction of the inventive method is preferably in 350～420 ℃ generally at 300～450 ℃; Reaction pressure is normal pressure or 0.005～0.07Mpa decompression or passes into the rare gas element such as nitrogen; The mass ratio of catalyzer and PS is generally 0.005～0.1: 1, be preferably 0.01～0.05: 1.
The present invention compares with traditional method, is characterized in: (1) has higher liquid yield and selectivity of styrene.(2) temperature of reaction is moderate.(3) catalyzer repetition reuse performance is good.
Specific implementation method
Below in conjunction with embodiment, method of the present invention is described further, but is not limitation of the invention.
Embodiment 1: 0.2g catalyst B aO/MCM-41 and 10g granules of polystyrene are added in reaction flask, under 0.01Mpa pressure, in 410 ℃ of reaction 0.5h, collect condensed product liquid and analyze with gas-chromatography.Transformation efficiency 98.5%, liquid yield 95.8%, in product liquid, styrene content is 80.1%.
Embodiment 2: experiment condition and step be with embodiment 1, just changes catalyzer into MgO/MCM-41, temperature of reaction changes 390 ℃ into, transformation efficiency 98.4%, and liquid yield 95.0%, in product liquid, styrene content is 80.1%.
Embodiment 3: experiment condition and step are with embodiment 1, just change 0.2g catalyst B aO/MCM-41 into 0.3g catalyzer CaO/MCM-41, temperature of reaction changes 400 ℃ into, transformation efficiency 98.7%, liquid yield 96.3%, in product liquid, styrene content is 80.5%.
Embodiment 4: experiment condition and step just change catalyzer into K with embodiment 1
2O-BaO/MCM-41, transformation efficiency 98.8%, liquid yield 96.6%, in product liquid, styrene content is 80.4%.
Embodiment 5: experiment condition and step just change catalyzer into K with embodiment 1
2O-MgO/MCM-41, reaction pressure changes 0.03Mpa into, transformation efficiency 99.0%, liquid yield 96.3%, in product liquid, styrene content is 80.6%.
Embodiment 6: 0.1g catalyst B aO/MCM-41 and 10g granules of polystyrene added in reaction flask, and under 0.05Mpa pressure, in 410 ℃ of reaction 1h, transformation efficiency 98.5%, liquid yield 94.1%, in product liquid, styrene content is 80.0%.
Embodiment 7: 0.2g catalyst B aO/MCM-41 and 10g granules of polystyrene added in reaction flask, and under 0.01Mpa pressure, in 370 ℃ of reaction 1h, transformation efficiency 98.5%, liquid yield 95.0%, in product liquid, styrene content is 80.2%.
Embodiment 8: 0.2g catalyzer MgO/MCM-41 and 10g granules of polystyrene added in reaction flask, passing under condition of nitrogen gas, and in 400 ℃ of reaction 0.5h, transformation efficiency 98.3%, liquid yield 95.1%, in product liquid, styrene content is 81.3%.
Embodiment 9-14: experiment condition and step just change catalyzer into embodiment 1 catalyzer that reclaims in embodiment 1, carry out repeating for 6 times the reuse experiment.The repetition reuse of catalyzer the results are shown in Table 1.
The repetition reuse result of table 1 catalyzer
Comparative example 1: experiment condition and step just change catalyzer into CaO with embodiment 1.Transformation efficiency 94.7%, liquid yield 92.3%, in product liquid, styrene content is 68.5%.
Comparative example 2: experiment condition and step just change catalyzer into MCM-41 with embodiment 1.Transformation efficiency 92.1%, liquid yield 90.7%, in product liquid, styrene content is 69.0%.
Claims (4)
1. a deposed polystyrene (PS) catalytic pyrolysis reclaims the method for styrene material, being about to useless PS and basic metal and/or alkali-earth metal modified MCM-41 intermediate pore molecular sieve catalyst adds in reactor by a certain percentage, in normal pressure or decompression or pass under condition of nitrogen gas, carry out at a certain temperature scission reaction, after reaction finishes, the gained product liquid obtains toluene, ethylbenzene and vinylbenzene aroamtic hydrocarbon raw material through distillation operation, and catalyzer is without any processing direct reuse.
2. method according to claim 1, wherein catalyzer used is the mesoporous molecular sieve MxO/MCM-41 that contains basic metal and/or alkaline-earth metal, wherein M is K, Mg, Ca, Ba alkali and alkaline earth metal ions or its mixture, x=1 or 2.
3. method according to claim 2, wherein the preparation of catalyzer can be adopted blending method or load method.
4. method according to claim 1, wherein scission reaction can be carried out under normal pressure, also can carry out under 0.005～0.07Mpa decompression, also can carry out passing under condition of nitrogen gas.
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|---|---|---|---|
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| CN101891581B true CN101891581B (en) | 2013-05-08 |
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| CN102617267A (en) * | 2012-03-14 | 2012-08-01 | 沈阳建筑大学 | Method for depolymerizing waste polystyrene and recovering monomer |
| CN113321566B (en) * | 2021-07-06 | 2024-04-09 | 洛阳理工学院 | Method for preparing bromostyrene by cracking brominated polystyrene |
| CN116272970A (en) * | 2023-03-28 | 2023-06-23 | 中国科学技术大学 | Cracking method of polystyrene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106371A (en) * | 1994-02-03 | 1995-08-09 | 杨先春 | Catalytic degradation of waste polystyrene into phenylethylene |
| CN1673206A (en) * | 2004-03-23 | 2005-09-28 | 陕西天星环保设备工程有限公司 | Method of recovering styrene as a chemical material from foamed polystyrene plastic |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106371A (en) * | 1994-02-03 | 1995-08-09 | 杨先春 | Catalytic degradation of waste polystyrene into phenylethylene |
| CN1673206A (en) * | 2004-03-23 | 2005-09-28 | 陕西天星环保设备工程有限公司 | Method of recovering styrene as a chemical material from foamed polystyrene plastic |
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