CN116328820A - Catalyst for high-yield light oil by cracking waste plastics and preparation method and application thereof - Google Patents
Catalyst for high-yield light oil by cracking waste plastics and preparation method and application thereof Download PDFInfo
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- CN116328820A CN116328820A CN202111585720.5A CN202111585720A CN116328820A CN 116328820 A CN116328820 A CN 116328820A CN 202111585720 A CN202111585720 A CN 202111585720A CN 116328820 A CN116328820 A CN 116328820A
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- molecular sieve
- catalyst
- usy molecular
- light oil
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 239000002699 waste material Substances 0.000 title claims abstract description 79
- 229920003023 plastic Polymers 0.000 title claims abstract description 73
- 239000004033 plastic Substances 0.000 title claims abstract description 73
- 238000005336 cracking Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 92
- 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 92
- 239000003921 oil Substances 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000004927 clay Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000004537 pulping Methods 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 238000010306 acid treatment Methods 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 49
- 238000012986 modification Methods 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- -1 rectorite Chemical compound 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 239000004743 Polypropylene Substances 0.000 claims description 25
- 229920001155 polypropylene Polymers 0.000 claims description 25
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000005995 Aluminium silicate Substances 0.000 claims description 23
- 235000012211 aluminium silicate Nutrition 0.000 claims description 23
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 13
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 229920001903 high density polyethylene Polymers 0.000 claims description 11
- 239000004700 high-density polyethylene Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229920001684 low density polyethylene Polymers 0.000 claims description 10
- 239000004702 low-density polyethylene Substances 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052621 halloysite Inorganic materials 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000011959 amorphous silica alumina Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 19
- 229920000098 polyolefin Polymers 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 238000004821 distillation Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001694 spray drying Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
Abstract
The invention relates to a preparation method of a catalyst for producing light oil by cracking waste plastics, which comprises the following steps: (1) Mixing USY molecular sieve and guiding agent according to the weight ratio of 5-20:1, reacting for 1-10 hours at 80-100 ℃, filtering and washing; (2) After the washed USY molecular sieve is subjected to acid treatment and sodium reduction, filtering and washing again, mixing the washed USY molecular sieve with a solution of modified metal, wherein the modified metal is calculated by metal simple substance, and the metal simple substance accounts for 0.1-1.0% of the dry basis weight of the USY molecular sieve; (3) Mixing the modified USY molecular sieve with clay and binder, pulping, drying and roasting to obtain the catalyst for cracking waste plastics and producing light oil. The invention also relates to a catalyst for the cracking of waste plastics to produce more light oil and application thereof. The preparation method provided by the invention can improve the accessibility of the diffusion mass transfer and the catalyst activity of the polyolefin macromolecule raw materials and products, and improve the yield of light oil prepared by cracking waste plastics.
Description
Technical Field
The invention belongs to the field of preparation of catalysts for cracking waste plastics and producing more light oil, and particularly relates to a catalyst for cracking waste plastics and producing more light oil as well as a preparation method and application thereof.
Background
Waste plastics in daily life garbage are called white garbage, which seriously endangers the living environment of human beings, and is also the most headache environmental treatment problem of governments of various countries. In recent years, there have been many reports on a method for producing an oil product by pyrolysis of waste plastics. In the process of cracking waste plastics to prepare oil products, a catalyst special for cracking waste plastics to prepare oil products becomes a research hot spot.
Chinese application CN200810036703.4 discloses a catalyst for preparing fuel oil by catalytic cracking of mixed waste plastics: the catalyst used in the first section waste plastic cracking process is metal oxide modified white clay or montmorillonite, which consists of 2.0wt% to 30.0wt% of metal oxide and 70.0wt% to 98.0wt% of white clay or montmorillonite, wherein the metal oxide is ferric oxide, aluminum oxide, magnesium oxide, lanthanum oxide, calcium oxide or copper oxide, and the metal oxide is singly used or a mixture of two of the metal oxide and the aluminum oxide is mixed according to the weight ratio of 1/10 to 10/1; the catalyst for catalytic cracking modification in the second section is a metal oxide modified mesoporous or macroporous molecular sieve, the modified metal oxide is ferric oxide, molybdenum oxide, zinc oxide, cerium oxide, lanthanum oxide, nickel oxide or copper oxide, and the modified oxide is singly used or two of the modified oxides are optionally used in a composite way, and the composite is according to the weight ratio of 1/10-10/1; the medium or large pore molecular sieve is selected from ZSM-5, MCM-22, USY, REY, beta or MOR molecular sieve with a silicon-aluminum ratio of 3-50, and is singly used or optionally used in combination according to a weight ratio of 1/10-10/1; the content of the modified metal oxide in the catalyst is 1.0wt% to 20.0wt%. The invention discloses a technical scheme of using USY of a mesoporous or macroporous molecular sieve as a catalyst for catalytic cracking modification of waste plastics after modification by zinc and copper.
Chinese application CN111099615a discloses a method for preparing mesoporous Y molecular sieve, which comprises mixing and contacting the Y molecular sieve with ordered mesoporous guiding agent to obtain mixed solution a, adding inorganic alkali solution B into the mixed solution a to obtain mixed solution C, washing the mixed solution C, and drying to obtain mesoporous molecular sieve. The technical scheme disclosed by the invention is that the Y molecular sieve is firstly contacted with the ordered mesoporous guiding agent in advance, the ordered mesoporous guiding agent enters into the pore canal of the Y molecular sieve, and then alkali treatment is carried out, so that the simple and efficient alkali treatment process is realized, and a large number of mesopores are introduced into the microporous molecular sieve.
Chinese application CN101168678A discloses a catalyst which can be used for cracking polyethylene and polypropylene waste plastics to prepare fuel oil. The modified kaolin is prepared from a KDC-1 molecular sieve and kaolin through phosphoric acid modification. The catalyst is used for cracking waste plastics, so that the cracking temperature is reduced, the polyethylene is reduced by about 100 ℃, the polypropylene is reduced by about 50 ℃, the yields of gasoline and diesel oil are improved to more than 80%, and the residue amount is reduced; the technical scheme disclosed by the invention is that a KDC-1 molecular sieve and kaolin are mixed, the mixture is put into a baking oven for drying, then quantitative phosphoric acid solution is added, stirring and standing are carried out, drying and roasting are carried out, and the molecular sieve and the kaolin are subjected to phosphorus modification in an impregnation mode.
Chinese application CN105214716a discloses a multi-stage pore molecular sieve catalyst for waste plastics conversion and its preparation method, the method is that micro-mesoporous composite MCM-41 molecular sieve containing ten-membered ring or twelve-membered ring microporous structure unit and binder are kneaded and formed, and then further modified, wherein the preparation method of the micro-mesoporous composite molecular sieve is as follows: the catalyst is prepared by using slurry or filtrate of alkali-treated microporous molecular sieve containing ten-membered rings or twelve-membered rings as a silicon-aluminum source or a part of silicon-aluminum source, using cetyl trimethyl ammonium bromide CTAB as a template agent and carrying out hydrothermal crystallization under certain conditions.
Chinese application CN103357431a discloses a method for preparing fuel catalyst for vehicle by cracking waste plastics, which comprises mixing small-grain rare earth-ZSM-5/ZSM-11 molecular sieve with binderFurther modifying the molded product to obtain the adhesive, wherein the adhesive is alumina or silica; the proportion of the molecular sieve and the binder is 30-85 wt%, znO accounts for 1.0-5.0 wt% and P accounts for the catalyst 2 O 5 The weight percentage is 0.5 to 6.0 percent; the technical proposal disclosed by the invention is that small-grain rare earth-ZSM-5/ZSM-11 molecular sieve is directly modified by zinc and phosphorus after being molded.
In summary, in the research of catalysts for catalytic conversion of waste plastics, the present focus is mainly on microporous molecular sieves such as HY, ZSM-5, beta, MOR and mesoporous molecular sieve catalysts such as MCM-41, and the microporous molecular sieves have good hydrothermal stability, good acidity and shape selectivity and are applied to catalytic pyrolysis of waste plastics to a certain extent. However, due to the structural limitation, polyolefin macromolecules can only react on the outer surface of the polyolefin macromolecules, and the utilization rate of acid sites on the inner surface is low; the mesoporous molecular sieves have larger pore diameters, provide favorable space for macromolecular reaction, but are not widely applied to polyolefin cracking reaction due to weaker acidity and stability.
Disclosure of Invention
The invention aims to solve the technical problems that the common USY molecular sieve in industry is used for pore construction, pore surface acidity modulation and metal modification, so that the diffusion mass transfer of polyolefin macromolecular raw materials and products and the accessibility of catalyst activity are improved, and the light oil yield is improved.
Therefore, the invention provides a preparation method of a catalyst for cracking waste plastics to produce light oil in a more productive way, which comprises the following steps:
(1) Mixing USY molecular sieve and a guiding agent according to the weight ratio of 5-20:1, wherein the USY molecular sieve is reacted for 1-10 hours at 80-100 ℃ on a dry basis, and filtering and washing;
(2) Performing acid treatment on the washed USY molecular sieve to reduce sodium, filtering again, washing with water, and mixing with a solution of modified metal, wherein the modified metal is calculated by metal simple substance, and the metal simple substance accounts for 0.1-1.0% of the dry basis weight of the USY molecular sieve; preferably, the acid treatment sodium reduction conditions are: the pH value is 2.0-3.0, the temperature is 80-100 ℃ and the time is 1-3 hours;
(3) Mixing the modified USY molecular sieve with clay and binder, pulping, drying and roasting to obtain the catalyst for cracking waste plastics and producing light oil.
In the preparation method of the invention, in the step (1), preferably, the weight ratio of the USY molecular sieve to the guiding agent is 10-16:1.
In the preparation method of the invention, in the step (1), the mixing reaction time of the USY molecular sieve and the guiding agent is preferably 4-8 hours.
In the preparation method of the invention, in the step (1), preferably, the liquid-solid ratio of the USY molecular sieve and the guiding agent after being mixed is 3-1.5:1.
According to the preparation method of the invention, the guiding agent in the step (1) is a common guiding agent, for example, the guiding agent is prepared according to the composition of the guiding agent in the embodiment 1 of CN1232862A, wherein preferably, the components are calculated according to the mass, and the composition of the guiding agent is as follows: (14-16) SiO 2 :(0.7～1.3)Al 2 O 3 :(14～16)Na 2 O:(300～330)H 2 O。
According to the preparation method, preferably, each component is one or more of chromium chloride, manganese chloride, zinc chloride and copper chloride according to the mass.
The preparation method of the invention, wherein the total specific surface area of the modified USY molecular sieve is preferably more than 650m 2 /g, external specific surface greater than 110m 2 Per gram, the total pore volume is greater than 0.50cm 3 /g, average pore size greater than 3.0nm; the total specific surface area of the USY molecular sieve before modification is 600-750m 2 Per gram, the external specific surface is 50-80m 2 Per gram, the total pore volume is 0.300-0.400cm 3 And/g, the average pore diameter is 2.0-2.8nm.
According to the preparation method disclosed by the invention, in the step (3), clay is selected from one or more of clay commonly used as a catalytic cracking catalyst component, wherein preferably, the clay is selected from one or more of kaolin, halloysite, acid extraction enhancement kaolin, alkali extraction enhancement kaolin, montmorillonite, kieselguhr, rectorite, halloysite, sepiolite and bentonite.
According to the preparation method disclosed by the invention, the binder in the step (3) is selected from one or more of binders commonly used in cracking catalysts, wherein the binder is preferably selected from one or more of silica sol, alumina sol, modified silica sol, modified alumina sol, amorphous silica alumina gel and pseudo-boehmite, and further preferably pseudo-boehmite and/or alumina sol.
The invention also provides a catalyst for producing light oil by cracking waste plastics, which is prepared by adopting the preparation method, and comprises, by mass of the catalyst, 100%, 5-30% of modified USY molecular sieve based on dry basis, 10-80% of clay based on dry basis and 5-40% of binder based on oxide; preferably, it contains 5 to 20% of modified USY molecular sieve on a dry basis, 20 to 65% of clay on a dry basis and 5 to 30% of binder on an oxide basis.
Therefore, the invention also provides a method for producing light oil by cracking waste plastics, which adopts the catalyst prepared by the preparation method, and the conditions of the cracking waste plastics are as follows: the temperature is 320-450 ℃, the pressure is 0.1-1.0 MPa, and the mass ratio of the catalyst to the waste plastic is 2-15 wt%.
The method for producing light oil by cracking waste plastic is characterized in that the waste plastic is preferably one or more selected from waste low-density polyethylene, high-density polyethylene, polypropylene and polystyrene; the relative molecular weight of the low-density polyethylene is 0.910-0.925, and the relative molecular weight of the high-density polyethylene is 0.941-0.965.
The beneficial effects of the invention are as follows:
(1) According to the preparation method of the catalyst, the USY molecular sieve and the guiding agent are mixed for reaction, the high alkalinity of the guiding agent is used for constructing a pore canal of the USY molecular sieve, crystal nuclei in the guiding agent are reacted with the surface active sites of the USY molecular sieve pore canal, the surface acidity of the pore canal can be modulated, the cracking capacity of the catalyst is increased, and after the USY molecular sieve is subjected to modification reaming and surface modulation by the guiding agent, metal ions are enabled to enter the pore canal more easily to generate metal hydroxyl during subsequent ion exchange, and the cracking, isomerization and other capacities of the catalyst are improved.
(2) The preparation method of the catalyst provided by the invention is modifiedThe total specific surface area of the USY is more than 650m 2 /g, external specific surface greater than 110m 2 Per gram, the total pore volume is greater than 0.50cm 3 And/g, the average pore diameter is larger than 3.0nm, the diffusion mass transfer of polyolefin macromolecular raw materials and products can be effectively promoted, the catalyst activity accessibility is good, the heat stability is good, and the light oil yield is high.
(3) At present, most of waste plastic catalytic cracking catalysts are in laboratory research stages, and industrial products are not reported yet. The catalyst provided by the invention is prepared from USY, clay and binder which are commonly used in industry on a pilot plant, has mature and simple process and is easy for industrial production.
In summary, the preparation method of the catalyst provided by the invention sequentially adopts the USY molecular sieve commonly used in industry to carry out guiding agent modification, acid modification and metal modification, wherein the metal modification adopts a mixed ion exchange mode instead of impregnation. The preparation method of the catalyst provided by the invention carries out pore construction through modification of the guiding agent, acid modification, pore surface acidity modulation and metal modification in a mixed ion exchange mode, can improve the diffusion mass transfer of polyolefin macromolecule raw materials and products and the accessibility of catalyst activity, and improves the yield of preparing light oil by cracking waste plastics.
The catalyst provided by the invention is used in the waste plastic cracking process, and has the characteristics of good accessibility of catalyst activity and high light oil yield.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and the experimental methods of specific conditions are not noted in the following examples, and generally, the% is weight% according to conventional conditions.
The raw material sources are as follows:
industrial USY molecular sieve (12.5% burning loss, total specific surface area 617.3 m) 2 Per gram, external specific surface 70.52m 2 Per gram, a total pore volume of 0.400cm 3 Per g, average pore size of 2.59 nm), industrial HY molecular sieve (17.6% burn, total ratio table)Area is 716.3m 2 Per gram, external specific surface 54.5m 2 Per gram, a total pore volume of 0.355cm 3 Per g, average pore diameter 2.12 nm), hydrochloric acid (36-37 m%), nitric acid (69 m%), kaolin (14.6% burn), diatomaceous earth (15.4% burn), aluminum sol (Al) 2 O 3 19.4%), pseudo-boehmite (17.0% burn off), water glass (SiO) 2 250g/L，Na 2 O90 g/L), high alkali (Al 2 O 3 281g/L，Na 2 O43 g/L), alkali liquor (14 w%) are industrial products, are obtained from catalyst factories of Lanzhou petrochemical company, and are produced by national pharmaceutical group, wherein sodium hydroxide, potassium hydroxide, chromium chloride, manganese chloride, zinc chloride and copper chloride are all analytically pure.
Evaluation analysis method:
the molecular sieve surface area and pore volume are determined by a low temperature nitrogen adsorption-desorption method, and the metal content of the molecular sieve is determined by a fluorescence method. (analytical methods see petrochemical analytical methods (RIPP Experimental methods), yang Cuiding et al, science Press, 1990) the catalyst reactivity was evaluated using a small fixed fluidized bed.
The invention provides a preparation method of a catalyst for cracking waste plastics to produce light oil in a more productive manner, which comprises the following steps:
(1) Mixing USY molecular sieve and a guiding agent according to the weight ratio of 5-20:1, wherein the USY molecular sieve is reacted for 1-10 hours at 80-100 ℃ on a dry basis, and filtering and washing;
(2) Performing acid treatment on the washed USY molecular sieve to reduce sodium, filtering again, washing with water, and mixing with a solution of modified metal, wherein the modified metal is calculated by metal simple substance, and the metal simple substance accounts for 0.1-1.0% of the dry basis weight of the USY molecular sieve;
(3) Mixing the modified USY molecular sieve with clay and binder, pulping, drying and roasting to obtain the catalyst for cracking waste plastics and producing light oil.
In some embodiments, it is preferred that the acid treatment sodium reduction conditions are: the pH value is 2.0-3.0, the temperature is 80-100 ℃ and the time is 1-3 hours.
In some embodiments it is preferred that the weight ratio of the USY molecular sieve to the directing agent is 10-16:1.
In some embodiments it is preferred that the USY molecular sieve is mixed with the directing agent for a reaction time of 4 to 8 hours.
In some embodiments, it is preferred that the USY molecular sieve and the directing agent be mixed at a liquid to solid ratio of 3-1.5:1.
According to the preparation method of the invention, the guiding agent in the step (1) is a common guiding agent, for example, the guiding agent is prepared according to the composition of the guiding agent in the embodiment 1 of CN1232862A, and in some embodiments, the components are preferably calculated according to the mass, and the composition of the guiding agent is as follows: (14-16) SiO 2 :(0.7～1.3)Al 2 O 3 :(14～16)Na 2 O:(300～330)H 2 O。
In some embodiments, it is preferable that the modified metal is one or more of chromium chloride, manganese chloride, zinc chloride, and copper chloride, based on the amount of the substance.
In some embodiments, it is preferred that the modified USY molecular sieve has a total specific surface area of greater than 650m 2 /g, external specific surface greater than 110m 2 Per gram, the total pore volume is greater than 0.50cm 3 /g, average pore size greater than 3.0nm; the total specific surface area of the USY molecular sieve before modification is 600-750m 2 Per gram, the external specific surface is 50-80m 2 Per gram, the total pore volume is 0.300-0.400cm 3 And/g, the average pore diameter is 2.0-2.8nm.
In the preparation method of the present invention, in the step (3), the clay is selected from one or more of clays commonly used as catalytic cracking catalyst components, and in some embodiments, preferably, the clay is selected from one or more of kaolin, halloysite, acid-pumping-improving kaolin, alkali-pumping-improving kaolin, montmorillonite, diatomaceous earth, rectorite, halloysite, sepiolite and bentonite.
According to the preparation method of the invention, the binder in the step (3) is selected from one or more of binders commonly used in cracking catalysts, and in some embodiments, the binder is preferably selected from one or more of silica sol, alumina sol, modified silica sol, modified alumina sol, amorphous silica alumina gel and pseudo-boehmite, and further preferably pseudo-boehmite and/or alumina sol.
The catalyst for the cracking of the waste plastics to produce the light oil is prepared by the preparation method, and comprises, by mass of the catalyst, 100%, 5-30% of modified USY molecular sieve based on dry basis, 10-80% of clay based on dry basis and 5-40% of binder based on oxide; preferably, it contains 5 to 20% of modified USY molecular sieve on a dry basis, 20 to 65% of clay on a dry basis and 5 to 30% of binder on an oxide basis.
The method for producing light oil by cracking waste plastics comprises the following steps of: the temperature is 320-450 ℃, the pressure is 0.1-1.0 MPa, and the mass ratio of the catalyst to the waste plastic is 2-15 wt%.
In some embodiments, it is preferable that the waste plastic is selected from one or more of waste low density polyethylene, high density polyethylene, polypropylene and polystyrene; the relative molecular weight of the low-density polyethylene is 0.910-0.925, and the relative molecular weight of the high-density polyethylene is 0.941-0.965.
Specific examples:
example 1
0.8kg of USY molecular sieve (dry basis), 0.16kg of directing agent (molar composition: 16 SiO) 2 :Al 2 O 3 :16Na 2 O:330H 2 O) and 1.60kg deionized water are uniformly mixed and reacted for 1.5 hours at 90 ℃, filtered and washed, then mixed with 1.3kg deionized water, the pH value is regulated to 2.20 by hydrochloric acid, the mixture is reacted for 1.1 hours at 93 ℃, filtered and washed, then mixed and stirred with 21g of chromium chloride and 3.69kg deionized water for 1 hour, wherein the total specific surface area of USY after modification is 660.9m 2 /g, external specific surface 113.3m 2 Per gram, a total pore volume of 0.512cm 3 And (3) mixing and pulping the mixture with 1.83kg of kaolin (dry basis), 0.222kg of pseudo-boehmite and 0.951kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the catalyst C-1 for cracking waste plastics and producing light oil.
The waste polypropylene is used as raw material, and the yield of light oil (distillation range is 30-350 ℃) is 87.2% under the reaction conditions that the temperature is 365 ℃, the pressure is 0.1MPa and the weight percent of catalyst to polypropylene is 9.0%.
Example 2
0.3kg of USY molecular sieve (dry basis), 0.03kg of directing agent (molar composition: 14 SiO) 2 :0.9Al 2 O 3 :15Na 2 O:320H 2 O) and 0.67kg deionized water are uniformly mixed and reacted for 5.5 hours at 95 ℃, filtered and washed, then mixed with 0.6kg deionized water, the pH value is regulated to 2.53 by hydrochloric acid, the reaction is carried out for 1.5 hours at 97 ℃, filtered and washed, then mixed and stirred with 5.67g zinc chloride and 3.96kg deionized water for 1 hour, wherein the total specific surface area of USY after modification is 657.6m 2 /g, external specific surface of 110.9m 2 Per gram, a total pore volume of 0.503cm 3 And (3) mixing and pulping the mixture with 2.1kg of kaolin (dry basis), 0.361kg of pseudo-boehmite and 0.773kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the catalyst C-2 for cracking waste plastics and producing light oil.
Waste plastics are used as raw materials (low-density polyethylene with relative molecular weight of 0.910-0.925, high-density polyethylene with relative molecular weight of 0.941-0.965, polypropylene: 20%, 32%, 46%), and under the reaction conditions of temperature 410 ℃, pressure 0.35MPa, catalyst: waste plastics=5.5wt%, the yield of light oil (distillation range is 30-350 ℃) is 86.2%.
Example 3
0.6kg of USY molecular sieve (dry basis), 0.038kg of directing agent (molar composition: 16 SiO) 2 :0.7Al 2 O 3 :14Na 2 O:330H 2 O) and 1.11kg deionized water are uniformly mixed and reacted for 4 hours at 85 ℃, filtered and washed, then mixed with 1.2kg deionized water, the pH value is regulated to 2.12 by hydrochloric acid, reacted for 2.1 hours at 92 ℃, filtered and washed, then mixed and stirred with 6.15g chromium chloride and 1.27g copper chloride 2.41kg deionized water for 1 hour, wherein the total specific surface area of USY after modification is 666.8m 2 Per gram, external specific surface 115.6m 2 Per gram, a total pore volume of 0.515cm 3 And (3) mixing and pulping the mixture with 1.2kg of diatomite (dry basis), 0.904kg of pseudo-boehmite and 2.32kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the catalyst C-3 for cracking waste plastics and producing light oil.
The waste plastic is used as raw materials (the mass percentage of low-density polyethylene with the relative molecular weight of 0.910-0.925 and high-density polyethylene, polypropylene and polystyrene with the relative molecular weight of 0.941-0.965 is 20%, 18%, 46% and 16%), and the yield of light oil (the distillation range is 30-350 ℃) is 87.6% under the reaction conditions that the temperature is 405 ℃, the pressure is 0.15MPa and the catalyst and the waste plastic are 9 wt%.
Example 4
0.9kg of USY molecular sieve (dry basis), 0.072kg of directing agent (molar composition: 15 SiO) 2 :Al 2 O 3 :15Na 2 O:300H 2 O) and 1.75kg deionized water are uniformly mixed and reacted for 8 hours at 100 ℃, filtered and washed, then mixed with 2.7kg deionized water, the pH value is regulated to 2.95 by hydrochloric acid, reacted for 3.0 hours at 80 ℃, filtered and washed, then mixed with 4.62g chromium chloride and 3.59kg deionized water and stirred for 1 hour, wherein the total specific surface area of USY after modification is 671.0m 2 Per gram, external specific surface is 123.3m 2 Per gram, a total pore volume of 0.521cm 3 And (3) mixing and pulping the mixture with 0.75kg of kaolin (dry basis), 1.37kg of pseudo-boehmite and 1.08kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the catalyst C-4 for cracking waste plastics and producing light oil.
The waste plastic is used as raw material (high density polyethylene with relative molecular weight of 0.941-0.965, polypropylene: 50%, 50%), and the yield of light oil (distillation range of 30-350 ℃) is 87.6% under the reaction conditions of 375 ℃ and 0.5MPa of pressure, 5wt% of catalyst and polypropylene.
Example 5
0.15kg of USY molecular sieve (dry basis), 0.008kg of directing agent (molar composition: 16 SiO) 2 :0.9Al 2 O 3 :15Na 2 O:330H 2 O) and 0.25kg deionized water are uniformly mixed and reacted for 9.5 hours at 90 ℃, filtered and washed, then mixed with 0.33kg deionized water, the pH value is regulated to 2.56 by hydrochloric acid, reacted for 1.5 hours at 92 ℃, filtered and washed, then mixed and stirred with 0.938g zinc chloride, 2.31g chromium chloride and 3.75kg deionized water for 1 hour, wherein the total specific surface area of the USY after modification is 656.6m 2 /g, external specific surface of 111.3m 2 Per gram, a total pore volume of 0.507cm 3 Per gram, the average pore diameter is 3.16nm, and then mixed with 1.4kg of kaolin (dry basis), 1.0kg of diatomite (dry basis), 0.542kg of pseudo-boehmite and 0.773kg of aluminum sol for pulping, and sprayingDrying and forming, roasting, washing, filtering and drying to obtain the catalyst C-5 for cracking waste plastics and producing light oil.
The waste plastic is used as raw material (polystyrene, polypropylene: 60wt%, 40 wt%) and the yield of light oil (distillation range is 30-350 ℃) is 87.1% under the reaction conditions of temperature 395 deg.C, pressure 0.5MPa, catalyst and polypropylene 4.5 wt%.
Comparative example 1
Mixing and stirring 0.8kg USY molecular sieve (dry basis), 21g chromium chloride and 3.69kg deionized water for 1h, mixing and pulping with 1.83kg kaolin (dry basis), 0.222kg pseudo-boehmite and 0.951kg aluminum sol, spray drying and molding, roasting, washing, filtering and drying to obtain the waste plastic cracking comparison catalyst D-1.
The waste polypropylene is used as raw material, and the light oil (distillation range is 30-350 ℃) yield is 81.6% under the reaction conditions that the temperature is 365 ℃, the pressure is 0.1MPa, and the catalyst and the polypropylene are 9.0 wt%.
Comparative example 2
Mixing and pulping 0.6kg USY molecular sieve (dry basis), 1.2kg diatomite (dry basis), 0.904kg pseudo-boehmite and 2.32kg aluminum sol, spray drying and forming, roasting, washing, filtering and drying to obtain the waste plastic cracking comparison catalyst D-2.
Waste plastics are used as raw materials (the mass percentages of low-density polyethylene with the relative molecular weight of 0.910-0.925, high-density polyethylene with the relative molecular weight of 0.941-0.965, polypropylene and polystyrene are 20%, 18%, 46% and 16%), and the yield of light oil (the distillation range is 30-350 ℃) is 80.1% under the reaction conditions that the temperature is 405 ℃, the pressure is 0.15MPa and the catalyst and the waste plastics are 9 wt%.
Comparative example 3
Mixing and pulping 0.15kg USY molecular sieve (dry basis) with 1.4kg kaolin (dry basis), 1.0kg diatomite (dry basis), 0.542kg pseudo-boehmite and 0.773kg aluminum sol, spray drying and molding, roasting, washing, filtering and drying to obtain the waste plastic cracking comparison catalyst D-3.
The waste plastic is used as raw material (polystyrene, polypropylene: 60%, 40%), and the yield of light oil (distillation range is 30-350 ℃) is 78.6% under the reaction conditions of 395 ℃ temperature, 0.5MPa pressure, catalyst: polypropylene=4.5 wt%.
Comparative example 4
0.8kg USY molecular sieve (dry basis), 0.16kg directing agent (molar composition: 16 SiO) 2 :Al 2 O 3 :16Na 2 O:330H 2 O) and 1.60kg deionized water are uniformly mixed and reacted for 1.5 hours at 90 ℃, filtered and washed, then mixed with 1.3kg deionized water, added with 0.28kg alkali liquor, reacted for 1.1 hours at 93 ℃, filtered and washed, then mixed and stirred with 21g of chromium chloride and 3.69kg deionized water for 1 hour, wherein the total specific surface area of USY after modification is 640.6m 2 /g, external specific surface of 101.3m 2 Per gram, a total pore volume of 0.432cm 3 And (3) mixing and pulping the mixture with 1.83kg of kaolin (dry basis), 0.222kg of pseudo-boehmite and 0.951kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the waste plastic cracking high-yield light oil catalyst D-4.
The waste polypropylene is used as raw material, and the light oil (distillation range is 30-350 ℃) yield is 70.8% under the reaction conditions of 365 ℃ and 0.1MPa and catalyst: polypropylene=9.0 wt%.
Comparative example 5
0.8kg of HY molecular sieve (dry basis), 0.16kg of directing agent (molar composition: 16 SiO) 2 :Al 2 O 3 :16Na 2 O:330H 2 O) and 1.60kg deionized water are uniformly mixed and reacted for 1.5 hours at 90 ℃, filtered and washed, then mixed with 1.3kg deionized water, the pH value is regulated to 2.20 by hydrochloric acid, the reaction is carried out for 1.1 hours at 93 ℃, filtered and washed, then mixed and stirred with 21g of chromium chloride and 3.69kg deionized water for 1 hour, wherein the total specific surface area of USY after modification is 570.3m 2 Per gram, external specific surface 70.5m 2 Per gram, a total pore volume of 0.328cm 3 And (3) mixing and pulping the mixture with 1.83kg of kaolin (dry basis), 0.222kg of pseudo-boehmite and 0.951kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the waste plastic cracking high-yield light oil catalyst D-5.
Waste plastics are used as raw materials (the mass percentages of low-density polyethylene with the relative molecular weight of 0.910-0.925, high-density polyethylene with the relative molecular weight of 0.941-0.965, polypropylene and polystyrene are 20%, 18%, 46% and 16%), and the yield of light oil (the distillation range is 30-350 ℃) is 71.1% under the reaction conditions that the temperature is 405 ℃, the pressure is 0.15MPa and the catalyst and the waste plastics are 9 wt%.
Comparative example 6
0.8kg of USY molecular sieve (dry basis), 0.16kg of directing agent (molar composition: 16 SiO) 2 :Al 2 O 3 :16Na 2 O:330H 2 O) and 1.60kg deionized water are uniformly mixed and reacted for 1.5 hours at 90 ℃, and 21g of chromium chloride is immersed after filtration and water washing, wherein the total specific surface area of the USY after modification is 653.1m 2 Per gram, external specific surface 103.7m 2 Per gram, a total pore volume of 0.478cm 3 And (3) mixing and pulping the mixture with 1.83kg of kaolin (dry basis), 3.69kg of deionized water, 0.222kg of pseudo-boehmite and 0.951kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the waste plastic cracking high-yield light oil catalyst D-6.
The waste plastic is used as raw material (polystyrene, polypropylene: 60%, 40%), and the light oil (distillation range is 30-350 ℃) yield is 80.7% under the reaction conditions of 395 ℃ temperature, 0.5MPa pressure, catalyst: polypropylene=4.5 wt%.
Comparative example 7
Mixing 0.8kg USY molecular sieve (dry basis) with 3.69kg deionized water, adjusting pH to 2.20 with hydrochloric acid, reacting at 93 deg.C for 1.1h, adding 21g chromium chloride, stirring for 1h, filtering, washing with water, mixing with 0.16kg guiding agent (molar composition: 16 SiO) 2 :Al 2 O 3 :16Na 2 O:330H 2 O) and 1.60kg deionized water are uniformly mixed and reacted for 1.5 hours at 90 ℃, and the mixture is filtered and washed with water, wherein the total specific surface area of the USY after modification is 650.3m 2 Per gram, external specific surface is 101.2m 2 Per gram, a total pore volume of 0.473cm 3 And (3) mixing and pulping the mixture with 1.83kg of kaolin (dry basis), 3.69kg of deionized water, 0.222kg of pseudo-boehmite and 0.951kg of aluminum sol, spray-drying, forming, roasting, washing, filtering and drying to obtain the waste plastic cracking and light oil production catalyst D-7.
The waste polypropylene is used as raw material, and the light oil (distillation range is 30-350 ℃) yield is 73.2% under the reaction conditions of 365 ℃ and 0.1MPa and catalyst: polypropylene=9.0 wt%.
As can be seen from the comparison of the above examples and comparative examples, the beneficial effects of the present invention are as follows:
(1) According to the preparation method of the catalyst, the USY molecular sieve and the guiding agent are mixed for reaction, the high alkalinity of the guiding agent is used for constructing a pore canal of the USY molecular sieve, crystal nuclei in the guiding agent are reacted with the surface active sites of the USY molecular sieve pore canal, the surface acidity of the pore canal can be modulated, the cracking capacity of the catalyst is increased, and after the USY molecular sieve is subjected to modification reaming and surface modulation by the guiding agent, metal ions are enabled to enter the pore canal more easily to generate metal hydroxyl during subsequent ion exchange, and the cracking, isomerization and other capacities of the catalyst are improved.
(2) The preparation method of the catalyst provided by the invention has the advantages that the total USY specific surface area after modification is more than 650m 2 /g, external specific surface greater than 110m 2 Per gram, the total pore volume is greater than 0.50cm 3 And/g, the average pore diameter is larger than 3.0nm, the diffusion mass transfer of polyolefin macromolecular raw materials and products can be effectively promoted, the catalyst activity accessibility is good, the heat stability is good, and the light oil yield is high.
(3) At present, most of waste plastic catalytic cracking catalysts are in laboratory research stages, and industrial products are not reported yet. The catalyst provided by the invention is prepared from USY, clay and binder which are commonly used in industry on a pilot plant, has mature and simple process and is easy for industrial production.
In summary, the preparation method of the catalyst provided by the invention sequentially adopts the USY molecular sieve commonly used in industry to carry out guiding agent modification, acid modification and metal modification, wherein the metal modification adopts a mixed ion exchange mode instead of impregnation. The preparation method of the catalyst provided by the invention carries out pore construction through modification of the guiding agent, acid modification, pore surface acidity modulation and metal modification in a mixed ion exchange mode, can improve the diffusion mass transfer of polyolefin macromolecule raw materials and products and the accessibility of catalyst activity, and improves the yield of preparing light oil by cracking waste plastics.
The catalyst provided by the invention is used in the waste plastic cracking process, and has the characteristics of good accessibility of catalyst activity and high light oil yield.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (12)
1. The preparation method of the catalyst for producing the light oil by cracking the waste plastics is characterized by comprising the following steps:
(1) Mixing USY molecular sieve and a guiding agent according to the weight ratio of 5-20:1, wherein the USY molecular sieve is reacted for 1-10 hours at 80-100 ℃ on a dry basis, and filtering and washing;
(2) Performing acid treatment on the washed USY molecular sieve to reduce sodium, filtering again, washing with water, and mixing with a solution of modified metal, wherein the modified metal is calculated by metal simple substance, and the metal simple substance accounts for 0.1-1.0% of the dry basis weight of the USY molecular sieve; preferably, the acid treatment sodium reduction conditions are: the pH value is 2.0-3.0, the temperature is 80-100 ℃ and the time is 1-3 hours;
(3) Mixing the modified USY molecular sieve with clay and binder, pulping, drying and roasting to obtain the catalyst for cracking waste plastics and producing light oil.
2. The method of claim 1, wherein in step (1), the weight ratio of the USY molecular sieve to the directing agent is 10-16:1.
3. The method of claim 1, wherein in step (1), the USY molecular sieve is mixed with the directing agent for a reaction time of 4 to 8 hours.
4. The method of claim 1, wherein in step (1), the USY molecular sieve is mixed with the directing agent at a liquid to solid ratio of 3-1.5:1.
5. The method of claim 1, wherein the components are in the form of a substanceThe composition of the guiding agent is as follows: (14-16) SiO 2 :(0.7～1.3)Al 2 O 3 :(14～16)Na 2 O:(300～330)H 2 O。
6. The preparation method according to claim 1, wherein each component is one or more of chromium chloride, manganese chloride, zinc chloride and copper chloride based on the amount of the substance.
7. The preparation method according to claim 1, wherein the total specific surface area of the modified USY molecular sieve is greater than 650m 2 /g, external specific surface greater than 110m 2 Per gram, the total pore volume is greater than 0.50cm 3 /g, average pore size greater than 3.0nm; the total specific surface area of the USY molecular sieve before modification is 600-750m 2 Per gram, the external specific surface is 50-80m 2 Per gram, the total pore volume is 0.300-0.400cm 3 And/g, the average pore diameter is 2.0-2.8nm.
8. The preparation method according to claim 1, wherein the clay is one or more selected from the group consisting of kaolin, halloysite, acid extraction-enhanced kaolin, alkali extraction-enhanced kaolin, montmorillonite, diatomaceous earth, rectorite, halloysite, sepiolite, and bentonite.
9. The preparation method according to claim 1, wherein the binder is selected from one or more of silica sol, alumina sol, modified silica sol, modified alumina sol, amorphous silica-alumina gel, pseudo-boehmite, preferably pseudo-boehmite and/or alumina sol.
10. A catalyst for the pyrolysis of waste plastics to produce more light oil, which is prepared by the preparation method of any one of claims 1 to 9, and is characterized in that the catalyst comprises, based on 100% of the catalyst mass, 5 to 30% of modified USY molecular sieve based on dry basis, 10 to 80% of clay based on dry basis and 5 to 40% of binder based on oxide; preferably, it contains 5 to 20% of modified USY molecular sieve on a dry basis, 20 to 65% of clay on a dry basis and 5 to 30% of binder on an oxide basis.
11. A method for producing light oil by cracking waste plastics, which is characterized in that the catalyst prepared by the preparation method of any one of claims 1-9 is adopted, and the conditions for cracking the waste plastics are as follows: the temperature is 320-450 ℃, the pressure is 0.1-1.0 MPa, and the mass ratio of the catalyst to the waste plastic is 2-15 wt%.
12. The method for producing light oil by cracking waste plastic according to claim 11, wherein the waste plastic is one or more selected from waste low density polyethylene, high density polyethylene, polypropylene and polystyrene; the relative molecular weight of the low-density polyethylene is 0.910-0.925, and the relative molecular weight of the high-density polyethylene is 0.941-0.965.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005094990A1 (en) * | 2004-03-30 | 2005-10-13 | Indian Oil Corporation Limited | A catalyst composition for catalytic cracking of waste plastic |
| CN101284235A (en) * | 2008-04-28 | 2008-10-15 | 同济大学 | Catalyst for catalytic cracking mixed waste plastic and preparation method thereof |
| CN101934234A (en) * | 2010-09-13 | 2011-01-05 | 中南大学 | Mesoporous molecular sieve catalyst for catalytic cracking of waste plastics as well as preparation method and application thereof |
| CN103301870A (en) * | 2012-03-09 | 2013-09-18 | 中国石油天然气股份有限公司 | Preparation method for catalytic cracking cocatalyst |
| CN104549448A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing light steam cracking raw materials by catalytic cracking |
| CN109433249A (en) * | 2018-08-21 | 2019-03-08 | 中国石油大学(华东) | A kind of method and its application of Y type molecular sieve structure directing agent modified aluminas |
| CN111686787A (en) * | 2020-06-10 | 2020-09-22 | 中国石油天然气集团有限公司 | Hydrocracking catalyst carrier, and preparation method and application thereof |
| WO2021204818A1 (en) * | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Waste plastic based oil upgrading into high value chemicals via direct catalytic cracking |
| CN113526522A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
| CN116265108A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst for producing more gasoline |
-
2021
- 2021-12-22 CN CN202111585720.5A patent/CN116328820A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005094990A1 (en) * | 2004-03-30 | 2005-10-13 | Indian Oil Corporation Limited | A catalyst composition for catalytic cracking of waste plastic |
| CN101284235A (en) * | 2008-04-28 | 2008-10-15 | 同济大学 | Catalyst for catalytic cracking mixed waste plastic and preparation method thereof |
| CN101934234A (en) * | 2010-09-13 | 2011-01-05 | 中南大学 | Mesoporous molecular sieve catalyst for catalytic cracking of waste plastics as well as preparation method and application thereof |
| CN103301870A (en) * | 2012-03-09 | 2013-09-18 | 中国石油天然气股份有限公司 | Preparation method for catalytic cracking cocatalyst |
| CN104549448A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing light steam cracking raw materials by catalytic cracking |
| CN109433249A (en) * | 2018-08-21 | 2019-03-08 | 中国石油大学(华东) | A kind of method and its application of Y type molecular sieve structure directing agent modified aluminas |
| WO2021204818A1 (en) * | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Waste plastic based oil upgrading into high value chemicals via direct catalytic cracking |
| CN113526522A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
| CN111686787A (en) * | 2020-06-10 | 2020-09-22 | 中国石油天然气集团有限公司 | Hydrocracking catalyst carrier, and preparation method and application thereof |
| CN116265108A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst for producing more gasoline |
Non-Patent Citations (3)
| Title |
|---|
| ABEL MINGORANCE-BAENA ET.AL: "Improved Catalytic Technology for Waste Plastic Processing: Toward Novel Remediation and Emission Control Measures", 《ACS SUSTAINABLE CHEM. ENG.》, 18 November 2018 (2018-11-18) * |
| 安杰;朱向学;李秀杰;王玉忠;陈福存;谢素娟;徐龙伢;: "废塑料在改性ZSM-5上裂解转化生产车用液体燃料", 化工进展, no. 1, 15 July 2012 (2012-07-15) * |
| 徐建春;李雪;付正祥;徐成华;刘建英;: "固体超强酸SO_4~2-/TiO_2-SiO_2催化废旧塑料裂解制燃油", 石油与天然气化工, no. 02, 15 April 2011 (2011-04-15) * |
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