CN1562947A - Method for producing benzoic acid by degrading waste plastic of polystyrene through catalysis in liquid phase - Google Patents
Method for producing benzoic acid by degrading waste plastic of polystyrene through catalysis in liquid phase Download PDFInfo
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- CN1562947A CN1562947A CNA200410017619XA CN200410017619A CN1562947A CN 1562947 A CN1562947 A CN 1562947A CN A200410017619X A CNA200410017619X A CN A200410017619XA CN 200410017619 A CN200410017619 A CN 200410017619A CN 1562947 A CN1562947 A CN 1562947A
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- manganese
- cobalt
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- used plastics
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 48
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 230000000593 degrading effect Effects 0.000 title claims abstract description 5
- 239000007791 liquid phase Substances 0.000 title claims description 21
- 239000004033 plastic Substances 0.000 title claims description 21
- 229920003023 plastic Polymers 0.000 title claims description 21
- 238000006555 catalytic reaction Methods 0.000 title claims description 20
- 239000005711 Benzoic acid Substances 0.000 title abstract 2
- 235000010233 benzoic acid Nutrition 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000012442 inert solvent Substances 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 38
- 239000010941 cobalt Substances 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 18
- 235000011054 acetic acid Nutrition 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000005609 naphthenate group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- HJUGFYREWKUQJT-UHFFFAOYSA-N carbon tetrabromide Natural products BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims description 2
- ZDUOUNIIAGIPSD-UHFFFAOYSA-N 1,1,1-tribromoethane Chemical compound CC(Br)(Br)Br ZDUOUNIIAGIPSD-UHFFFAOYSA-N 0.000 claims description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 241001074085 Scophthalmus aquosus Species 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- HJUGFYREWKUQJT-OUBTZVSYSA-N tetrabromomethane Chemical group Br[13C](Br)(Br)Br HJUGFYREWKUQJT-OUBTZVSYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 20
- 239000002904 solvent Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000003965 capillary gas chromatography Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In this invention method, waste polystyrene is used as raw material, using soluble cobalt salt, manganic salt and bromide as catalysts, and using inert solvent. They are proportionally mixed under temp. of 100 to 350 deg.C, and pressure of 0.4 to 4.0 MPa. Oxygen-contained gas is used for oxidizing and degrading waste polystyrene to produce benzoic acid. Advantages are: mild reaction condition, high reaction rate, high yield, good economic and social benefits.
Description
Technical field
The invention discloses a kind of liquid-phase catalysis degraded polystyrene waste or used plastics and produce benzoic method.
Background technology
Polystyrene (PS) material and polystyrene foamed (EPS) material have the performance of many excellences, thus be widely used in the manufacturing and the packaging field of various product, as instrument, household electrical appliances, fast food and supermarket etc.But after waste and old product of these polystyrene or disposable product become rubbish,, thereby form " white pollution " that ecotope is constituted a serious threat because of its unreactiveness with height is difficult for by microbiological degradation.Up to now, the main method of handling discarded PS is existing a lot, mainly contains methods such as landfill method, burning method, cyclic regeneration method and degraded utilization.
Adopting liquid-phase catalysis atmospheric oxidation technology degrading waste polystyrene is a brand-new process.In fact, macromolecular materials such as polystyrene all can slowly carry out the autoxidation reaction with air and natural degradation becomes low molecular compound under ultraviolet irradiation, and its natural degradation mechanism is very similar to organic liquid-phase catalytic oxidation mechanism.As sophisticated liquid-phase catalysis atmospheric oxidation technology (US2245528), be widely used at present the synthetic and preparation of industrial chemicals such as organic acid, aldehyde, ketone, pure and mild phenol, advantages such as this technology has that the three wastes are few, mild condition, production capacity are big, highly selective and high reaction rate, representing the development trend of oxygen-bearing organic matter synthesis technique, so can adopt liquid-phase catalysis air oxidation process simulating nature degradation process, waste and old polystyrol is degraded to low-molecular-weight organic compound.
The degraded utilization research of waste and old polystyrene plastics is carried out early, and existing many relevant patents are come out.The research of this aspect mainly concentrates on thermal destruction and heterogeneous catalyst degraded aspect, and the molecular sieve catalytic thermo-cracking system oil tech of polystyrene has also been obtained significant progress (US48516101, US5078385, CN1097431 and CN1106371).In heterogeneous catalyst heat scission reaction process, it is to be solved also to exist many problems to have, as conducting heat carbon distribution, catalytic regeneration and recovery problem; Also have coal-fired dust, waste gas, waste residue and the processing wastewater that produces to cause secondary pollution problems on the other hand.
Summary of the invention
The object of the present invention is to provide a kind of high degradation rate, degradation condition gentleness, liquid-phase catalysis degraded polystyrene waste or used plastics that selectivity is high to produce benzoic method, use the pollution problem that this method not only can solve the polystyrene waste or used plastics, be used for producing the phenylformic acid product but also can turn waste into wealth.
The inventive method is to be catalyzer with solubility cobalt salt, manganese salt and bromide, it is mixed with polyethylene waste or used plastics and inert solvent, under the pressure condition of 100～350 ℃ temperature and 0.4～4.0Mpa, adopt the gas that contains oxygen molecule that waste and old polystyrol is carried out oxidative degradation and produce phenylformic acid.
The inventive method may further comprise the steps:
1) waste and old polystyrol or polystyrene foamed are divided into the particle that particle diameter is 1～10mm;
2) be catalyzer with solubility cobalt salt, manganese salt and bromide ternary complex, catalyzer, polyethylene waste or used plastics are mixed with inert solvent, be added to and carry out oxidative degradation in the reactor, the mass ratio of inert solvent and polyethylene waste or used plastics is 1～50: 1, the catalyzer total concn is 50～10000ppm, wherein, the mol ratio of cobalt/manganese is 0.1～100, and the mol ratio of bromine/(cobalt+manganese) is 0.1～10;
3) under nitrogen protection, make temperature of reaction reach 100～350 ℃ with the temperature rise rate of 10～30 ℃/min, after reaction pressure reaches 0.4～4.0Mpa, feed the compression oxygen-containing gas, oxidative degradation is cooled to normal temperature after finishing, liquid-solid mixture;
4) liquid-solid mixture after will degrading filters, and the solid filter cake that filtration is obtained is washed again, and purification process promptly gets phenylformic acid.And filtrate can be used as solvent and catalyst system continues to recycle.
Solubility cobalt salt in the above-mentioned catalyzer can be selected from the acetate of cobalt, the formate of cobalt, the naphthenate of cobalt, the bromide of cobalt, the muriate of cobalt, the carbonate of cobalt, the nitrate of cobalt or the vitriol of cobalt.Preferred Cobalt diacetate tetrahydrate.Soluble manganese salt can be selected from the acetate of manganese, the formate of manganese, the naphthenate of manganese, the bromide of manganese, the muriate of manganese, the carbonate of manganese, the nitrate of manganese or the vitriol of manganese.Preferred four water acetic acid manganese.Soluble bromide can be selected from tetrabromomethane, methenyl bromide, methylene bromide, tetrabromoethane, tribromoethane, ethylene dibromide, bromobenzene, hydrogen bromide, brometo de amonio, bromination is received or Potassium Bromide.
Among the present invention, the preferred 100～5000ppm of total concn of solubility cobalt salt, manganese salt and bromide ternary complex catalyst.The mol ratio of cobalt/manganese preferred 0.2～20.The mol ratio preferred 0.5～2 of bromine/(cobalt+manganese).
Among the present invention, said inert solvent is the aliphatic carboxylic acid inert solvent that contains 1-6 carbon atom, can be selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, Succinic Acid, pentanedioic acid, butanic acid, hexanodioic acid or trimethylacetic acid.Usually, be to improve degradation rate, can adopt that to add mass ratio in the aliphatic carboxylic acid inert solvent be 2～25% water, or to add mass ratio be that 5～50% aromatic hydrocarbon or derivatives thereof is as solubility promoter.Said aromatic hydrocarbon or derivatives thereof can be benzene, toluene or halogeno-benzene.
The preferred temperature of oxidative degradation of the present invention is 185～200 ℃, and preferred pressure is 1.5～2.5MPa.
The oxygen-containing gas that uses among the present invention can be pure oxygen or oxygen and noble gas mixtures, as the gaseous mixture of carbonic acid gas and nitrogen, more preferably air.
The present invention can improve polystyrene oxidative degradation process by changing the composition of degradation temperature and solvent system, adjusts the yield of degradation rate and phenylformic acid product.
The inventive method is a solvent with the aliphatic carboxylic acid that contains 1-6 carbon atom, with the aromatic hydrocarbon or derivatives thereof is solubility promoter, under suitable reaction temperature and pressure condition, in cobalt-manganese-bromine catalyst system, adopt the gas that contains oxygen molecule that waste and old polystyrol is carried out oxidative degradation and produce phenylformic acid.This method reaction conditions gentleness, speed of reaction is fast, the yield height, the social benefit that not only has solution " white pollution " problem, and can the output phenylformic acid etc. fine chemical material to obtain high economic benefit, it is low to have the degraded expense, degradation products added value advantages of higher.
Embodiment
Below will set forth the present invention in more detail by embodiment.
Embodiment 1
To volume is that 500 milliliters of titanium material autoclaves add the liquid-solid reaction mixtures, feeds nitrogen as protection gas, and with reaction mixture heat temperature raising to 190 ℃, pressure rises to 2.0MPa when stirring.The liquid-solid reaction mixture consist of 300g acetic acid, 10.4g polystyrene solid and 3.75g catalyzer.The catalyzer that is added consists of: 0.76g Cobalt diacetate tetrahydrate, 0.76g four water acetic acid manganese and 2.23g hydrogen bromide (aqueous solution of 47% concentration).DeR is carried out under 190 ℃ of pressure 2.0MPa of temperature condition, feeds high-pressure air in the reaction process continuously, and the constant air flow is 8L/min.Finish reaction after 120 minutes,, can measure the composition of its oxidative degradation small molecules product the capillary gas chromatography analysis of reaction solution sample.The instrument that is adopted is Tianjin, island GC-9A gas chromatograph of being furnished with fid detector, carries out data logging and processing with MR-95 chromatographic data workstation; Chromatographic column, stationary phase EC-5, thickness 1.0 μ m, 30m * 0.32mm; Adopt programmed temperature method, 160 ℃ keep 2min, and 30 ℃/min is warming up to 280 ℃, keeps 5min.Can get each degradable component by chromatographic peak area data and correction factor and compare concentration data with the quality of solvent acetic acid, because of solvent acetic acid basic unreactiveness that keeps in reaction system, it is constant that the acetic acid quality can be thought, can calculate the generation total mass of each component by reinforced acetic acid quality and each constituent mass specific concentration data.The result shows that the main small molecules product of polystyrene liquid-phase catalysis degraded has phenylformic acid and diphenylthanedione etc.Wherein mainly be phenylformic acid, react that benzoic yield can reach 32% after 120 minutes, the result sees table 1 and table 2 for details.
Embodiment 2
The mode identical with embodiment 1 carried out the oxidative degradation of polystyrene, and just the solvent system that is adopted in embodiment 2 is the mixture of acetic acid and water, and solvent composition is 276g acetic acid and 24g water.Degrade after 120 minutes and to finish reaction, with capillary gas chromatography can measure the growing amount of oxidative breakdown products such as phenylformic acid and diphenylthanedione, the results are shown in Table 1.
Embodiment 3
The mode identical with embodiment 1 carried out the oxidative degradation of polystyrene, and just the solvent system that is adopted in embodiment 3 is the mixture of acetic acid and benzene, and solvent composition is 270g acetic acid and 30g benzene.Degrade after 120 minutes and to finish reaction, with capillary gas chromatography can measure the growing amount of oxidative breakdown products such as phenylformic acid and diphenylthanedione, the results are shown in Table 1 and table 2.
Embodiment 4
The mode identical with embodiment 1 carried out the oxidative degradation of polystyrene, and just the solvent system that is adopted in embodiment 4 is the mixture of acetic acid and benzene, and solvent composition is 150g acetic acid and 150g benzene.Degrade after 120 minutes and to finish reaction, with capillary gas chromatography can measure the growing amount of oxidative breakdown products such as phenylformic acid and diphenylthanedione, the results are shown in Table 1.
DeR result under the table 1 different solvents system composition condition
| Example | Solvent composition acetic acid: water: benzene (g: g: g) | Temperature (℃) | Phenylformic acid (g) | Diphenylthanedione (g) | Phenylformic acid yield (%) * |
| ??1 | ?300∶0∶0 | ??190 | ????3.95 | ??0.078 | ???32.4 |
| ??2 | ?276∶24∶0 | ??190 | ????4.35 | ??0.043 | ???35.7 |
| ??3 | ?270∶0∶30 | ??190 | ????8.21 | ??0.105 | ???67.3 |
| ??4 | ?150∶0∶150 | ??190 | ????9.6 | ??0.102 | ???78.7 |
* phenylformic acid yield (%) is meant that actual phenylformic acid growing amount accounts for benzene ring of polystyrene and all is converted into
The per-cent of the theoretical growing amount of the phenylformic acid of phenylformic acid phenyl ring.
Compare with embodiment 1, the result of embodiment 2 shows, the existence of acetate solvate system tolerable less water molecule, an amount of water concentration also help polystyrene liquid-phase catalysis degradation process (the phenylformic acid yield by 32.4% of example 1 be increased to example 2 35.7%).The result of comparative example 1, embodiment 3 and embodiment 4 as can be known, polystyrene liquid-phase catalysis degradation process has been quickened in the adding of solubility promoter benzene effectively.Add 10% benzene solubility promoter, can make phenylformic acid yield be multiplied (being increased to 67.3.7%) by 32.4%; When the benzene that adds 50% was made solubility promoter, the polystyrene degraded generated benzoic yield and just can reach about 80%.Its dominant mechanism is, benzene can be strengthened the dissolving of polystyrene solid significantly as a kind of solubility promoter, eliminated the dissolving diffusion-controlled step of degradation process effectively, made the oxidative degradation process be reduced to a homogeneous catalysis oxidation reaction process, thereby quickened degradation process.
Embodiment 5
The mode identical with embodiment 1 carried out the oxidative degradation of polystyrene, and just degradation temperature and the pressure condition that is adopted in embodiment 5 is different, and the degradation temperature that embodiment 5 is adopted is that 160 ℃ of pressure are 1.0MPa.Degrade after 120 minutes and to finish reaction, with capillary gas chromatography can measure the growing amount of oxidative breakdown products such as phenylformic acid, diphenylthanedione and phenol, the results are shown in Table 2.
Embodiment 6
The mode identical with embodiment 2 carried out the oxidative degradation of polystyrene, and just degradation temperature and the pressure condition that is adopted in embodiment 6 is different, and the degradation temperature that embodiment 6 is adopted is that 160 ℃ of pressure are 1.0MPa.Degrade after 120 minutes and to finish reaction, with capillary gas chromatography can measure the growing amount of oxidative breakdown products such as phenylformic acid, diphenylthanedione and phenol, the results are shown in Table 2.
DeR result under table 2 condition of different temperatures
| Example | Temperature (℃) | Solvent composition acetic acid: water: benzene (g: g: g) | Phenylformic acid (g) | Diphenylthanedione (g) | Phenol (10-3g) | Phenylformic acid yield (%) * |
| ??1 | ??190 | ???300∶0∶0 | ??3.95 | 0.078 | ???0 | ?32.4 |
| ??5 | ??160 | ???300∶0∶0 | ??1.79 | 0.003 | ???＜1 | ?14.7 |
| ??3 | ??190 | ???270∶0∶30 | ??3.95 | 0.078 | ???0 | ?32.4 |
| ??6 | ??160 | ???270∶0∶30 | ??2.91 | 0.011 | ???1 | ?23.9 |
* phenylformic acid yield (%) is meant that actual phenylformic acid growing amount accounts for benzene ring of polystyrene and all is converted into
The per-cent of the theoretical growing amount of the phenylformic acid of phenylformic acid phenyl ring.
As shown in Table 2, the reduction of DeR temperature can make the polystyrene degradation process sharply slow down.Its reason may be the activity that low temperature has reduced chain reaction on the one hand, has generated the free radical terminator phenol that is unfavorable for DeR on the other hand.
The present invention can improve polystyrene oxidative degradation process by the ratio that improves degradation temperature and increase solvent system solubility promoter, and degradation rate is accelerated, and increases the yield of phenylformic acid product significantly.At different waste and old polystyrol reactants, can make degradation condition reach optimization by the adjusting of catalyzer, solvent and temperature.
Claims (10)
1, a kind of liquid-phase catalysis degraded polystyrene waste or used plastics is produced benzoic method, it is characterized in that may further comprise the steps:
1) waste and old polystyrol or polystyrene foamed are divided into the particle that particle diameter is 1～10mm;
2) be catalyzer with solubility cobalt salt, manganese salt and bromide ternary complex, catalyzer, polyethylene waste or used plastics are mixed with inert solvent, be added to and carry out oxidative degradation in the reactor, the mass ratio of inert solvent and polyethylene waste or used plastics is 1～50: 1, the catalyzer total concn is 50～10000ppm, wherein, the mol ratio of cobalt/manganese is 0.1～100, and the mol ratio of bromine/(cobalt+manganese) is 0.1～10;
3) under nitrogen protection, make temperature of reaction reach 100～350 ℃ with the temperature rise rate of 10～30 ℃/min, after reaction pressure reaches 0.4～4.0Mpa, feed the compression oxygen-containing gas, oxidative degradation is cooled to normal temperature after finishing, liquid-solid mixture;
4) liquid-solid mixture after will degrading filters, and the solid filter cake that filtration is obtained is washed again, and purification process promptly gets phenylformic acid.
2, liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 1 is produced benzoic method, it is characterized in that said inert solvent is the aliphatic carboxylic acid inert solvent that contains 1-6 carbon atom, is selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, Succinic Acid, pentanedioic acid, butanic acid, hexanodioic acid or trimethylacetic acid.
3. liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 2 is produced benzoic method, it is characterized in that it is 2～25% water that said aliphatic carboxylic acid inert solvent contains mass ratio.
4. liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 2 is produced benzoic method, it is characterized in that in said aliphatic carboxylic acid inert solvent adding mass ratio and be 5～50% aromatic hydrocarbon or derivatives thereof as solubility promoter.
5, liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 4 is produced benzoic method, it is characterized in that said aromatic hydrocarbon or derivatives thereof is benzene, toluene or halogeno-benzene.
6. liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 1 is produced benzoic method, it is characterized in that the solubility cobalt salt in the catalyzer is selected from the nitrate of the carbonate of the muriate of the bromide of the naphthenate of the formate of the acetate of cobalt, cobalt, cobalt, cobalt, cobalt, cobalt, cobalt or the vitriol of cobalt; Soluble manganese salt is selected from the acetate of manganese, the formate of manganese, the naphthenate of manganese, the bromide of manganese, the muriate of manganese, the carbonate of manganese, the nitrate of manganese or the vitriol of manganese; Soluble bromide is selected from tetrabromomethane, methenyl bromide, methylene bromide, tetrabromoethane, tribromoethane, ethylene dibromide, bromobenzene, hydrogen bromide, brometo de amonio, bromination is received or Potassium Bromide.
7. liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 1 is produced benzoic method, it is characterized in that in the said catalyzer, and the mol ratio of its brill/manganese is 0.2～20, and the mol ratio of bromine/(cobalt+manganese) is 0.5～2.
8. liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 1 is produced benzoic method, and the total concn that it is characterized in that catalyzer is 100～5000ppm.
9. liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 1 is produced benzoic method, and the temperature that it is characterized in that oxidative degradation is 185～200 ℃.
10. liquid-phase catalysis degraded polystyrene waste or used plastics according to claim 1 is produced benzoic method, and the pressure that it is characterized in that oxidative degradation is 1.5～2.5MPa.
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Cited By (4)
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| CN101279906B (en) * | 2007-12-27 | 2010-08-25 | 浙江科技学院 | Method for producing acetic acid by liquid phase catalytic degradation of waste polypropylene plastic |
| CN103555354A (en) * | 2013-10-22 | 2014-02-05 | 惠州市神州创宇低碳技术发展有限公司 | Method for refining oil through depolymerizing and liquifying waste plastics and device used in method |
| CN112961047A (en) * | 2021-03-03 | 2021-06-15 | 贵州大学 | Method for synthesizing benzoic acid by photo-thermal catalytic selective oxidation of polystyrene |
| CN113321579A (en) * | 2021-05-27 | 2021-08-31 | 中山大学 | Oxidative degradation method of aryl-containing polymer and application thereof |
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| US10259769B2 (en) * | 2017-07-13 | 2019-04-16 | David Lee Sikkenga | Conversion of polystyrene to benzoic acid |
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| DE69323125T2 (en) * | 1992-06-29 | 1999-08-19 | Mortimer Technology Holdings Ltd. | Process for the conversion of polymers |
| DE4328188C2 (en) * | 1993-08-21 | 1996-04-18 | Hoechst Ag | Process for the production of synthesis gas |
| DE4335972A1 (en) * | 1993-10-21 | 1995-04-27 | Basf Ag | Process for the recovery of styrene from used polystyrene |
| CN1133858A (en) * | 1995-04-21 | 1996-10-23 | 杨先春 | Catalyst for catalytic degradation of waste polystyrene plastics into styrene |
| CN1150956A (en) * | 1995-11-23 | 1997-06-04 | 杨亚力 | Catalyst for disposal of plastic waste |
| DE19641743B4 (en) * | 1996-10-10 | 2004-04-01 | Cet-Umwelttechnik-Entwicklungsgesellchaft Mbh | Process for the recovery of liquid fuels from polyolefin waste |
| US6031142A (en) * | 1997-09-11 | 2000-02-29 | Ponsford; Thomas E. | Alternative solvents for a method of reclaiming styrene and other products from polystyrene based materials |
| CN1250063A (en) * | 1999-03-09 | 2000-04-12 | 北京市海淀区中大环境技术研究所 | Waste polystyrene plastic treating method |
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| CN101279906B (en) * | 2007-12-27 | 2010-08-25 | 浙江科技学院 | Method for producing acetic acid by liquid phase catalytic degradation of waste polypropylene plastic |
| CN103555354A (en) * | 2013-10-22 | 2014-02-05 | 惠州市神州创宇低碳技术发展有限公司 | Method for refining oil through depolymerizing and liquifying waste plastics and device used in method |
| CN103555354B (en) * | 2013-10-22 | 2015-04-01 | 惠州市神州创宇低碳技术发展有限公司 | Method for refining oil through depolymerizing and liquifying waste plastics and device used in method |
| CN112961047A (en) * | 2021-03-03 | 2021-06-15 | 贵州大学 | Method for synthesizing benzoic acid by photo-thermal catalytic selective oxidation of polystyrene |
| CN112961047B (en) * | 2021-03-03 | 2023-07-25 | 贵州大学 | Method for synthesizing benzoic acid by photo-thermal catalytic selective oxidation of polystyrene |
| CN113321579A (en) * | 2021-05-27 | 2021-08-31 | 中山大学 | Oxidative degradation method of aryl-containing polymer and application thereof |
| CN113321579B (en) * | 2021-05-27 | 2023-08-11 | 中山大学 | Oxidative degradation method of aryl-containing polymer and application thereof |
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