CN114713268A - Molecular sieve catalyst for cracking waste plastic, preparation method thereof and waste plastic cracking method - Google Patents
Molecular sieve catalyst for cracking waste plastic, preparation method thereof and waste plastic cracking method Download PDFInfo
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- CN114713268A CN114713268A CN202110011768.9A CN202110011768A CN114713268A CN 114713268 A CN114713268 A CN 114713268A CN 202110011768 A CN202110011768 A CN 202110011768A CN 114713268 A CN114713268 A CN 114713268A
- Authority
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- China
- Prior art keywords
- molecular sieve
- cracking
- catalyst
- kaolin
- composite material
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 239000002699 waste material Substances 0.000 title claims abstract description 91
- 229920003023 plastic Polymers 0.000 title claims abstract description 90
- 239000004033 plastic Substances 0.000 title claims abstract description 90
- 238000005336 cracking Methods 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 76
- 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 abstract description 69
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 65
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 239000004927 clay Substances 0.000 claims abstract description 10
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 29
- -1 rectorite Chemical compound 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 16
- 229920001684 low density polyethylene Polymers 0.000 claims description 8
- 239000004702 low-density polyethylene Substances 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 7
- 239000004700 high-density polyethylene Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920002994 synthetic fiber Polymers 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 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 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000002609 medium Substances 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 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 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007320 rich medium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a molecular sieve catalyst for cracking waste plastics and a preparation method thereof. The preparation method of the molecular sieve catalyst for cracking the waste plastics comprises the following steps: (1) mixing the roasted kaolin, the water glass, the guiding agent and the alkali liquor to prepare Na with the raw material molar ratio of (5-10)2O∶Al2O3∶(8～25)SiO2∶(80～380)H2Crystallizing O at 90-95 ℃ for 16-32 hours, filtering, washing and drying to obtain a NaY molecular sieve composite material; (2) modifying the NaY molecular sieve composite material obtained in the step (1) according to a two-way two-baking process to obtain a modified molecular sieve composite material; (3) mixing the modified molecular sieve composite material, clay, binder and transition metal, pulping, and spray drying to obtain the waste plastic cracking materialThe invention also relates to a cracking method of waste plastics.
Description
Technical Field
The invention relates to a molecular sieve catalyst for waste plastic cracking and a preparation method and application thereof, in particular to a catalytic cracking catalyst containing a NaY molecular sieve and kaolin composite material and a preparation method thereof.
Background
With the progress of petroleum technology, the development of plastic industry provides various plastic products for human beings, and the plastic is widely applied to multiple industries of national economy and has penetrated into every corner of society due to the advantages of light weight, corrosion resistance, easy processing and forming, low cost, convenient use and the like. However, with the vigorous development and large-scale use of the plastic industry, waste plastic products and plastic wastes also bring about serious social problems. The recycling of waste plastics is always an important issue in the field of environmental protection and resource regeneration because of the reasons of large discarded amount, difficult degradation, difficult treatment, wide influence and the like, and the recycling of waste plastics is a major concern in the field of environmental protection and resource regeneration.
At present, catalysts are generally added in the cracking and conversion of waste plastics to crack and modify macromolecular raw materials, the content of heavy components in oil products is reduced through the catalytic action, and gasoline components, isomeric hydrocarbons and aromatic hydrocarbons are increased, so that the performance of the catalysts directly determines the yield and quality of the oil products, and the catalysts are the technical key of a cracking and conversion method and also are important factors for limiting the technical development of preparing fuel oil by cracking waste plastics.
Patent CN104056613A discloses a method for preparing a catalyst for catalytic cracking of waste plastics, which comprises adding water glass solution into sulfuric acid solution under vigorous stirring to make the concentration of silica reach 3.5% -6% to prepare acidic silica gel slurry; after adjusting the temperature and the pH, curing the slurry to obtain a silica gel structure suitable for serving as a catalyst framework; and adding an aluminum sulfate solution into the slurry, depositing aluminum on the silica hydrogel by using ammonia water, filtering the obtained silica hydrogel, washing by using a dilute ammonium chloride solution at the same time, removing adsorbed sodium, and drying to obtain the silica hydrogel. The specific characteristics and the effects of the use of the catalyst are not described in this patent.
Patent CN107413347A discloses a composite catalyst for plastic cracking, which is prepared from the following raw materials in parts by weight: 30-50 parts of calcium oxide, 1-3 parts of ferric trioxide, 3-7 parts of silicon dioxide, 3-7 parts of aluminum oxide, 30-50 parts of graphite and 1-5 parts of a lubricant; the catalyst of the invention can effectively prevent secondary pollution generated in the plastic cracking process and improve the working efficiency of plastic cracking.
Patent CN101168678A discloses a catalyst which can be used for preparing fuel oil by cracking polyethylene and polypropylene waste plastics. It is prepared by modifying KDC-1 type molecular sieve and kaolin through phosphoric acid. The method is characterized in that: 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 yield of gasoline and diesel oil is improved to more than 80 percent, and the residue amount is reduced.
Patent applicationCN103357431A discloses a preparation method of a catalyst for producing vehicle fuel by cracking waste plastics, which is prepared by molding a small-grain rare earth-ZSM-5/ZSM-11 molecular sieve and a binder and then further modifying the molded product, wherein the binder is alumina or silica; the proportion of the molecular sieve and the binder is 30-85 wt%, the weight percentage of ZnO in the catalyst is 1.0-5.0 wt%, and P2O5The weight percentage of the component is 0.5 to 6.0wt percent.
The patent CN1570028A discloses a plastic cracking catalyst and a preparation method thereof, wherein the catalyst comprises 50-65 wt% of fly ash, 15-30 wt% of aluminum chloride, 15-30 wt% of aluminum silicate and 0.5-2 wt% of ammonium molybdate, and the catalyst is obtained by crushing the fly ash and uniformly mixing the crushed fly ash with the aluminum chloride, the aluminum silicate and the ammonium molybdate. The above-mentioned plastic cracking catalyst can be added into the waste plastics, polyurethane or polystyrene foam which is melted into liquid so as to make them be cracked into fuel oil meeting the standard.
Patent CN105214716A discloses a hierarchical pore molecular sieve catalyst for waste plastic conversion and a preparation method thereof, the method is obtained by kneading a micro-mesoporous composite MCM-41 molecular sieve containing ten-membered ring or twelve-membered ring microporous structural units with a binder, and then further modifying the kneaded product, wherein the preparation method of the micro-mesoporous composite molecular sieve comprises the following steps: the preparation method is characterized in that slurry or filtrate of microporous molecular sieve containing ten-membered ring or twelve-membered ring is treated by alkali to be a silicoaluminum source or a part of the silicoaluminum source, Cetyl Trimethyl Ammonium Bromide (CTAB) is used as a template agent, and the microporous molecular sieve is prepared by hydrothermal crystallization under certain conditions. The catalyst is used in the process of producing the vehicle fuel by cracking and converting the waste plastics, can effectively promote the diffusion and mass transfer of macromolecular raw materials and products, has high utilization rate of acid sites, good hydrothermal stability and regeneration performance, and better performance of producing the clean vehicle fuel by cracking and converting the polyolefin waste plastics.
The catalyst for cracking waste plastics mainly comprises metal salt, metal oxide, molecular sieve or modified molecular sieve catalyst and the like, wherein the molecular sieve catalyst shows better catalytic cracking activity. For the reaction of catalytic cracking polyolefin by molecular sieve, because the polymer molecules are too large to enter the inside of the molecular sieve pore canal for reaction, firstly, the polyolefin in molten state reacts with the external specific surface active center of the molecular sieve. When the molecule of the first cracking reaction product is small enough, the product can diffuse into the active center inside the molecular sieve pore canal to carry out the second cracking reaction such as beta-chain scission, isomerization, aromatization and the like, so that the molecular sieve catalyst is required to have larger external specific surface area and a medium-large pore structure. The existing waste plastic conversion catalyst has the problems of low catalytic efficiency, short service life, easy inactivation, high cost and the like, and in addition, the preparation method of the waste plastic cracking catalyst is immature, so that the reports on the aspect are less. Therefore, it is very necessary to provide a molecular sieve catalyst for plastic cracking, which has low cost, high plastic cracking efficiency and good economic benefit.
Disclosure of Invention
The invention aims to provide a molecular sieve catalyst for cracking waste plastics and a preparation method and application thereof. The molecular sieve catalyst is a NaY molecular sieve composite material which is synthesized by kaolin in-situ crystallization and has rich medium and large pore structures, can effectively promote the diffusion mass transfer of polyolefin macromolecular raw materials and products, has high utilization rate of active sites, has good hydrothermal stability, does not use any template agent in the synthesis process, and has low cost.
The catalyst is prepared by modifying NaY molecular sieve composite material synthesized by kaolin in-situ crystallization through rare earth, mixing with clay, binder and transition metal, pulping, and spray drying. The medium-large pore volume of the NaY molecular sieve composite material accounts for more than 35 percent of the total pore volume, and the external specific surface area is 100m2More than g.
The invention provides a preparation method of a molecular sieve catalyst for cracking waste plastics, which comprises the following steps: (1) mixing the roasted kaolin, the water glass, the guiding agent and the alkali liquor to prepare Na with the raw material molar ratio of (5-10)2O∶Al2O3∶(8～25)SiO2∶(80～380)H2Crystallizing O at 90-95 ℃ for 16-32 hours, filtering, washing and drying to obtain a NaY molecular sieve composite material; (2) the NaY molecular sieve composite material in the step (1) is prepared according to the industrial common diplexModifying by a secondary baking process to obtain a modified molecular sieve composite material; (3) mixing and pulping the modified molecular sieve composite material, clay, binder and transition metal, and spray drying to obtain the molecular sieve catalyst for cracking the waste plastics.
The preparation method of the molecular sieve catalyst for waste plastic cracking provided by the invention preferably comprises the step (1) that kaolin comprises soft kaolin, hard kaolin and coal gangue, the bit diameter of the kaolin is 2.5-3.5 mu m, the content of crystal kaolinite is higher than 80%, the content of iron oxide is lower than 1.7%, the sum of sodium oxide and potassium oxide is lower than 0.5%, and the kaolin is roasted at 700-1000 ℃ for 1-3 hours to form roasted kaolin.
In the preparation method of the molecular sieve catalyst for cracking waste plastics, the directing agent in the step (1) is only required to be a common directing agent, for example, the directing agent is prepared according to the directing agent composition in example 1 of CN1232862A, and the preferred material molar ratio composition of the directing agent recommended by the invention is as follows: (14-16) SiO2:(0.7～1.3)Al2O3:(14～16)Na2O:(300～330)H2And O, preferably, the addition amount of the guiding agent is 1 to 10 percent of the weight of the synthetic material, wherein the synthetic material refers to the sum of all raw materials used for synthesizing the NaY molecular sieve composite material in the step (1).
The preparation method of the molecular sieve catalyst for cracking waste plastics provided by the invention is characterized in that preferably, the alkali liquor in the step (1) is sodium hydroxide solution, and the addition amount of the alkali liquor accounts for 1% -6% of the weight of the synthetic material in terms of sodium hydroxide dry basis, and more preferably 2% -4%.
The preparation method of the molecular sieve catalyst for cracking waste plastics provided by the invention is preferably that the medium-large pore volume of the NaY molecular sieve composite material in the step (1) accounts for more than 35% of the total pore volume, and the external specific surface area is 100m2More than g.
In the preparation method of the NaY molecular sieve composite material, the post-modification of the composite material is preferably performed according to a commonly used industrial two-way baking process (jianlei, rule research of rare earth and NaY molecular sieve in a filter cake exchange process, master thesis of petrochemical science research institute, 2001), and the modification process is well known to those skilled in the art.
The method for preparing a molecular sieve catalyst for cracking waste plastics according to the present invention is preferably such that the clay is selected from one or more of clays commonly used as catalytic cracking catalyst components, such as one or more of kaolin, halloysite, acid-extracted kaolin, alkali-extracted kaolin, montmorillonite, diatomaceous earth, rectorite, halloysite, sepiolite and bentonite, which are well known to those skilled in the art.
The preparation method of the molecular sieve catalyst for cracking waste plastics provided by the invention is preferably that the binder is selected from one or more of the binders commonly used in cracking catalysts, such as one or more of silica sol, aluminum sol, modified silica sol, modified aluminum sol, amorphous silica-alumina gel and pseudo-boehmite, and further preferably pseudo-boehmite and/or aluminum sol.
In the preparation method of the molecular sieve catalyst for cracking waste plastics, the transition metal is preferably one or more of nitrates of chromium, cobalt and zinc.
The invention also provides a catalyst prepared by the preparation method of the waste plastic cracking molecular sieve catalyst, which comprises 30-70% of modified NaY molecular sieve composite material calculated by dry basis, 10-60% of clay calculated by dry basis, 5-40% of binder calculated by oxide and 0.1-2% of transition metal calculated by oxide, wherein the mass of the catalyst is 100%; preferably, the catalyst comprises, by mass, 100% of the modified NaY molecular sieve composite material in a dry basis 35-60%, clay in a dry basis 20-50%, binder in an oxide basis 5-30%, and transition metal in an oxide basis 0.1-1%.
The invention also provides a waste plastic cracking method, namely the application of the catalyst, the catalyst is used in the waste plastic cracking process, the cracking conditions are that the cracking temperature is 320-450 ℃, the pressure is 0.1-1.0 MPa, and the dosage of the catalyst is 2-15 wt% of the mass of the waste plastic.
In the application of the catalyst provided by the invention, preferably, the waste plastics is one or more of waste low-density polyethylene, high-density polyethylene, polypropylene and polystyrene.
The invention aims to provide a molecular sieve catalyst for waste plastic cracking and a preparation method thereof, wherein a NaY molecular sieve composite material takes kaolin as a raw material and adopts an in-situ crystallization technology to simultaneously generate a molecular sieve and a matrix, and the molecular sieve and the matrix are combined in a chemical bond-like manner, so that the catalyst has higher thermal and hydrothermal stability; part of SiO in kaolin during crystallization2And Al2O3The dissolution leads the surface to form rich medium-large pore structures, and the Y-shaped molecular sieve grows on the inner and outer surfaces of the kaolin, so that the kaolin has good accessibility of macromolecules, and the cracking activity of the catalyst to the macromolecules is increased; the large specific heat performance of the substrate in the composite material is very important for the heat transfer during the regeneration and cracking of the catalyst and the heat storage capacity required during large-scale catalytic cracking, and meanwhile, the acidity of the catalyst is modulated by adding transition metal, so that the cracking of waste plastics is facilitated. Therefore, the NaY molecular sieve composite material prepared into the waste plastic cracking catalyst has high cracking efficiency, good hydrothermal stability and low cost. The catalyst provided by the invention is used in the cracking process of waste plastics, and has the characteristics of good catalyst activity and high light oil yield.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Source of raw materials
1. Kaolin: the medium particle size is 3.2 μm, the kaolinite content is 82%, the iron oxide content is 0.74%, and the sum of the potassium oxide content and the sodium oxide content is 0.35%. A guiding agent: prepared according to the directing agent composition in CN1232862A example 1.
2. Water glass (SiO)2 250.3g/L，Na2O87.4 g/L), alkali liquor (NaOH 14 m%), kaolin (causticity 14.6%), diatomite (causticity 15.4%), alumina sol (Al)2O319.4%), pseudo-boehmite (reduced by 17.0%), rare earth nitrate (RE)2O3230.5g/L) are all industrial products, and are collected from catalyst factories of Lanzhou petrochemical company; chromium nitrate, cobalt nitrate and zinc nitrate are all chemically pure and produced by Yongda chemical reagents Limited in Tianjin.
Analytical method
The contents of rare earth and sodium oxide of the modified composite material are determined by adopting a fluorescence method, and the pore volume and the external surface area of the composite material are determined by adopting a low-temperature nitrogen adsorption-desorption method. (see "analytical methods in petrochemical industry (RIPP methods of experiments"), Yanggui et al, ed. science publishers, 1990), catalytic performance was evaluated using a small fixed fluidized bed (Huidetri Ji Co., Ltd., model FFB-200, Beijing).
Example 1
Roasting kaolin at 900 ℃ for 2 hours to obtain roasted kaolin, uniformly mixing 4kg of the roasted kaolin, 14.7kg of water glass, 1.4kg of a guiding agent and 5.3kg of alkali liquor, crystallizing at 92 ℃ for 24 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. Total pore volume of the composite material 0.46m3G, mesopore and macropore volume of 0.22m3Per g, external specific surface area 106.9m2(ii) in terms of/g. Modifying the NaY molecular sieve composite material prepared by the method according to a two-way two-baking process, wherein RE in the modified composite material2O3The content of Na is 4.04 percent2The O content was 1.11%. 1.7kg of kaolin (dry basis), 2.74kg of modified NaY molecular sieve composite material (dry basis), 3.26kg of alumina sol, 0.035kg of chromium nitrate and 7.5kg of deionized water are mixed, pulped, spray-dried, molded, roasted, washed, filtered and dried to obtain the molecular sieve catalyst C-1 for cracking the waste plastics.
The yield of light oil is 85.6% by using waste polypropylene as raw material and reacting at 355 deg.C and 0.1MPa with 6 wt% of catalyst and polypropylene.
Example 2
Will be highRoasting kaolin at 750 ℃ for 2.8 hours to obtain roasted kaolin, uniformly mixing 2.9kg of roasted kaolin, 4.6kg of sodium silicate, 0.75kg of guiding agent and 5.12kg of alkali liquor, crystallizing at 91 ℃ for 30 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. Total pore volume of the composite material 0.44m3(g), the pore volume of the medium and large pores is 0.19m3Per g, external specific surface area 101.3m2(ii) in terms of/g. Modifying the NaY molecular sieve composite material prepared by the method according to a two-way two-baking process, wherein RE in the modified composite material2O3Content of Na is 1.86%2The O content was 1.21%. 2.53kg of diatomite (dry basis), 1.57kg of modified NaY molecular sieve composite material (dry basis), 2.39kg of alumina sol, 0.55kg of pseudo-boehmite, 0.159kg of chromium nitrate, 0.09kg of cobalt nitrate and 7.1kg of deionized water are mixed, pulped, spray-dried and formed, roasted, washed, filtered and dried to obtain the molecular sieve catalyst C-2 for waste plastic cracking.
The yield of light oil is 83.4% by using waste low-density polyethylene as raw material and reacting at 425 deg.C and 0.3MPa with 12 wt% of catalyst and waste plastics.
Example 3
Roasting kaolin at 850 ℃ for 2 hours to obtain roasted kaolin, uniformly mixing 2.6kg of the roasted kaolin, 10.3kg of sodium silicate, 1.3kg of a guiding agent and 2.9kg of alkali liquor, crystallizing at 95 ℃ for 17 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. The total pore volume of the composite material is 0.45m3Per g, medium and large pore volume of 0.20m3G, external specific surface area 103.5m2(ii) in terms of/g. Modifying the NaY molecular sieve composite material prepared by the method according to a two-way two-baking process, wherein RE in the modified composite material2O3The content of Na is 8.28 percent2The O content was 1.13%. 1.12kg of kaolin (dry basis), 0.89kg of diatomite (dry basis), 2.28kg of modified NaY molecular sieve composite material (dry basis), 1.57kg of alumina sol, 0.253kg of zinc nitrate and 7.3kg of deionized water are mixed and pulped, spray-dried and formed, and the molecular sieve catalyst C-3 for cracking the waste plastics, which is prepared by the method, is obtained by roasting, washing, filtering and drying.
The light oil yield is 85.1% by taking waste plastics as raw materials (the mass percentages of low-density polyethylene, high-density polyethylene, polypropylene and polystyrene are 20%, 18%, 46% and 16%), and reacting at 400 ℃ and 0.1MPa under the condition that the weight percentage of catalyst and waste plastics is 10%.
Example 4
Roasting kaolin at 950 ℃ for 1.5 hours to obtain roasted kaolin, uniformly mixing 3.8kg of the roasted kaolin, 14.0kg of sodium silicate, 1.2kg of a guiding agent and 5.1kg of alkali liquor, crystallizing at 92 ℃ for 24 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. Total pore volume of the composite material 0.46m3Per g, medium and large pore volume of 0.23m3Per g, external specific surface area 103.9m2(iv) g. Modifying the NaY molecular sieve composite material prepared by the method according to a two-way two-baking process, wherein RE in the modified composite material2O3The content of Na is 4.21%2The O content was 1.01%. 0.9kg of kaolin (dry basis), 1.2kg of modified NaY molecular sieve composite material (dry basis), 4.62kg of alumina sol, 0.058kg of cobalt nitrate and 5.6kg of deionized water are mixed and pulped, and the molecular sieve catalyst C-4 for cracking the waste plastics is obtained by spray drying molding, roasting, washing, filtering and drying.
The yield of light oil is 84.6% by using waste polypropylene as raw material and reacting at 375 deg.C and 0.5MPa with 5 wt% of catalyst and polypropylene.
Example 5
Roasting kaolin at 870 ℃ for 2.2 hours to obtain roasted kaolin, uniformly mixing 2.9kg of the roasted kaolin, 10kg of silica sol, 1.1kg of a directing agent and 3.7kg of alkali liquor, crystallizing at 90 ℃ for 16 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. Total pore volume of the composite material 0.44m3(g), the pore volume of the medium and large pores is 0.21m3G, external specific surface area 109.1m2(ii) in terms of/g. The NaY molecular sieve composite material prepared by the method is modified according to a double-exchange double-baking process, and RE in the modified composite material2O3The content of Na is 3.75 percent2The O content was 1.11%. Mixing 1.8kg of kaolin (dry basis), 0.9kg of modified NaY molecular sieve composite material (dry basis), 1.55kg of alumina sol, 0.136kg of chromium nitrate, 0.077kg of cobalt nitrate, 0.073kg of zinc nitrate and 8.1kg of deionized water, pulping, and performing spray dryingAnd (3) forming, roasting, washing, filtering and drying to obtain the molecular sieve catalyst C-5 for cracking the waste plastics.
The light oil yield is 85.6% by taking waste polypropylene and low-density polyethylene (mass percent is 1: 1) as raw materials under the reaction conditions that the temperature is 410 ℃, the pressure is 0.8MPa, and the catalyst and the polypropylene are 7 wt%.
Example 6
Roasting kaolin for 1.8 hours at 920 ℃ to obtain roasted kaolin, uniformly mixing 3.0kg of the roasted kaolin, 19.2kg of silica sol, 1.74kg of a directing agent and 3.45kg of alkali liquor, crystallizing for 14 hours at 93 ℃, filtering, washing and drying to obtain the NaY molecular sieve composite material. Total pore volume of the composite material 0.43m3(g), the pore volume of the medium and large pores is 0.19m3Per g, external specific surface area 101.5m2(iv) g. Modifying the NaY molecular sieve composite material prepared by the method according to a two-way two-baking process, wherein RE in the modified composite material2O3The content of Na was 3.91%2The O content was 1.23%. 0.6kg of kaolin (dry basis), 1.65kg of modified NaY molecular sieve composite material (dry basis), 3.86kg of alumina sol, 0.077kg of zinc nitrate and 6.1kg of deionized water are mixed and pulped, and the mixture is subjected to spray drying forming, roasting, washing, filtering and drying to obtain the molecular sieve catalyst C-6 for cracking the waste plastics.
The light oil yield is 83.7% by using waste polypropylene and high density polyethylene (mass percent is 1: 1) as raw materials under the reaction conditions of temperature 330 ℃, pressure 0.8MPa and catalyst and polypropylene of 9 wt%.
Example 7
The method comprises the steps of roasting kaolin for 2.8 hours at 800 ℃ to obtain roasted kaolin, uniformly mixing 2.73kg of the roasted kaolin, 18.6kg of sodium silicate, 1.41kg of a guiding agent and 4.59kg of alkali liquor, crystallizing for 14.5 hours at 94.5 ℃, filtering, washing and drying to obtain the NaY molecular sieve composite material. The total pore volume of the composite material is 0.41m3Per g, medium and large pore volume of 0.17m3G, external specific surface area 105.7m2(ii) in terms of/g. Modifying the NaY molecular sieve composite material prepared by the method according to a two-way two-baking process, wherein RE in the modified composite material2O3The content of Na is 4.87%2O content of 103%. 1.35kg of kaolin (dry basis), 1.5kg of modified NaY molecular sieve composite material (dry basis), 0.78kg of alumina sol, 0.307kg of chromium nitrate and 9.6kg of deionized water are mixed, pulped, spray-dried, molded, roasted, washed, filtered and dried to obtain the molecular sieve catalyst C-7 for cracking the waste plastics.
The yield of light oil is 82.9% by using waste low-density polyethylene and high-density polyethylene (mass percent is 1: 1) as raw materials under the reaction conditions of 350 ℃, 0.9MPa of pressure and 8 wt% of catalyst and polypropylene.
Example 8
The method comprises the steps of roasting kaolin at 980 ℃ for 1.2 hours to obtain roasted kaolin, uniformly mixing 1.32kg of the roasted kaolin, 8.19kg of sodium silicate, 0.51kg of a guiding agent and 2.28kg of alkali liquor, crystallizing at 92 ℃ for 17 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. The total pore volume of the composite material is 0.42m3Per g, medium and large pore volume of 0.17m3G, external specific surface area 108.8m2(iv) g. Modifying the NaY molecular sieve composite material prepared by the method according to a two-way two-baking process, wherein RE in the modified composite material2O3The content of Na is 4.31%2The O content was 1.16%. 1.2kg of kaolin (dry basis), 1.2kg of modified NaY molecular sieve composite material (dry basis), 3.09kg of alumina sol, 0.102kg of chromium nitrate, 0.055 of zinc nitrate and 6.9kg of deionized water are mixed and pulped, spray-dried and formed, and the molecular sieve catalyst C-7 for cracking the waste plastics is obtained after roasting, washing, filtering and drying.
The light oil yield is 83.4% by using waste high density polyethylene as raw material and reacting at 375 deg.C and 0.65MPa with 6 wt% catalyst and polypropylene.
Comparative example 1
The NaY molecular sieve is modified by the second-exchange second-baking process according to the modification method in the example 1, and the modified molecular sieve RE2O3The content of Na is 3.96 percent2The O content was 1.19%. Mixing and pulping 1.7kg of kaolin (dry basis), 2.74kg of modified NaY molecular sieve (dry basis), 3.26kg of alumina sol, 0.035kg of chromium nitrate and 7.5kg of deionized water, spray drying and forming, roasting, washing, filtering and drying to obtain the modified NaY modified kaolin-based alumina composite materialThe prepared molecular sieve catalyst D-1 for cracking the waste plastics.
The yield of light oil is 79.8% by using waste polypropylene as raw material and reacting at 355 deg.C and 0.1MPa with 6 wt% of catalyst and polypropylene.
Comparative example 2
The NaY molecular sieve is modified by the double-exchange double-baking process according to the modification method in the embodiment 2, and RE in the modified molecular sieve2O3The content of Na is 1.69%2The O content was 1.24%. 2.53kg of diatomite (dry basis), 1.57kg of modified NaY molecular sieve (dry basis), 2.39kg of alumina sol, 0.55kg of pseudo-boehmite, 0.159kg of chromium nitrate, 0.09kg of cobalt nitrate and 7.1kg of deionized water are mixed, pulped, spray-dried and formed, roasted, washed, filtered and dried to obtain the molecular sieve catalyst D-2 for cracking the waste plastics.
The yield of light oil is 78.6% by using waste low-density polyethylene as raw material and reacting at 425 deg.C and 0.3MPa with 12 wt% of catalyst and waste plastics.
Comparative example 3
The NaY molecular sieve is modified by the second-exchange second-baking process according to the modification method in the embodiment 3, and RE in the modified molecular sieve2O3The content of Na is 8.07 percent2The O content was 1.15%. 1.12kg of kaolin (dry basis), 0.89kg of diatomite (dry basis), 2.28kg of modified NaY molecular sieve (dry basis), 1.57kg of alumina sol, 0.253kg of zinc nitrate and 7.3kg of deionized water are mixed and pulped, spray-dried and formed, and the molecular sieve catalyst D-3 for cracking the waste plastics, which is prepared by the method, is obtained by roasting, washing, filtering and drying.
The yield of light oil is 79.2% under the reaction conditions of 400 ℃ of temperature, 0.1MPa of pressure and 10 wt% of catalyst and waste plastics by taking waste plastics as raw materials (the mass percentages of low-density polyethylene, high-density polyethylene, polypropylene and polystyrene are 20%, 18%, 46% and 16%).
Comparative example 4
The NaY molecular sieve is modified by the second-cross-second baking process according to the modification method in the embodiment 4, and RE in the modified composite material2O3The content of Na is 4.01 percent2The O content was 1.17%. 0.9kg of kaolin (dry basis), 1.2kg of modified NaY molecular sieve (dry basis), 4.62kg of alumina sol, 0.058kg of cobalt nitrate and 5.6kg of deionized water are mixed, pulped, spray-dried, molded, roasted, washed, filtered and dried to obtain the molecular sieve catalyst D-4 for cracking waste plastics.
The yield of light oil is 78.6% by using waste polypropylene as raw material and reacting at 375 deg.C and 0.5MPa with 5 wt% of catalyst and polypropylene.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (14)
1. A preparation method of a molecular sieve catalyst for waste plastic cracking is characterized by comprising the following steps: (1) mixing the roasted kaolin, the water glass, the guiding agent and the alkali liquor to prepare Na with the raw material molar ratio of (5-10)2O∶Al2O3∶(8～25)SiO2∶(80～380)H2Crystallizing O at 90-95 ℃ for 16-32 hours, filtering, washing and drying to obtain a NaY molecular sieve composite material; (2) modifying the NaY molecular sieve composite material obtained in the step (1) according to a double-cross double-baking process to obtain a modified molecular sieve composite material; (3) and mixing and pulping the modified molecular sieve composite material, clay, a binder and transition metal, and spray-drying to obtain the molecular sieve catalyst for cracking the waste plastics.
2. The method of claim 1, wherein in step (1), the NaY molecular sieve composite has a mesopore volume of 35% or more of the total pore volume and an external specific surface area of 100m2More than g.
3. The method for preparing a molecular sieve catalyst for waste plastic cracking according to claim 1, wherein in step (1), the kaolin comprises soft kaolin, hard kaolin and coal gangue, the bit diameter of the kaolin is 2.5-3.5 μm, the content of crystalline kaolinite is higher than 80%, the content of iron oxide is lower than 1.7%, the sum of sodium oxide and potassium oxide is lower than 0.5%, and the kaolin is calcined at 700-1000 ℃ for 1-3 hours to form calcined kaolin.
4. The method of producing a molecular sieve catalyst for cracking waste plastics according to claim 1, wherein in step (1), the mass molar ratio composition of the directing agent is: (14-16) SiO2:(0.7～1.3)Al2O3:(14～16)Na2O:(300～330)H2And O, the addition amount of the guiding agent is 1-10% of the weight of the synthetic material, and the synthetic material refers to the sum of all raw materials used for synthesizing the NaY molecular sieve composite material in the step (1).
5. The method for preparing a molecular sieve catalyst for cracking waste plastic according to claim 1, wherein in step (1), the alkali solution is sodium hydroxide solution, and the addition amount is 1-6% of the weight of the synthesized material based on the dry basis of sodium hydroxide.
6. The method of claim 5, wherein in step (1), the alkali solution is a sodium hydroxide solution, and the amount added is 2-4% by weight of the synthesized material, based on the dry basis of sodium hydroxide.
7. The method of claim 1, wherein in step (3), the clay is selected from one or more of kaolin, halloysite, acid-extracted kaolin, alkali-extracted kaolin, montmorillonite, diatomaceous earth, rectorite, halloysite, sepiolite, and bentonite.
8. The method of preparing a molecular sieve catalyst for waste plastic cracking according to claim 1, wherein in step (3), the binder is selected from one or more of silica sol, aluminum sol, modified silica sol, modified aluminum sol, amorphous silica-alumina gel, and pseudo-boehmite.
9. The method of producing a molecular sieve catalyst for cracking waste plastics according to claim 1, wherein in step (3), the binder is selected from pseudo-boehmite and/or an aluminum sol.
10. The method of producing a molecular sieve catalyst for cracking waste plastics according to claim 1, wherein in step (3), the transition metal is selected from one or more nitrates of chromium, cobalt, and zinc.
11. A molecular sieve catalyst for waste plastic cracking, which is produced by the method according to any one of claims 1 to 10, characterized in that the catalyst comprises, by mass, 100%: the content of the modified NaY molecular sieve composite material is 30-70% in terms of dry basis, the content of clay is 10-60% in terms of dry basis, the content of a binder is 5-40% in terms of oxide, and the content of a transition metal is 0.1-2% in terms of oxide.
12. The molecular sieve catalyst for cracking waste plastic according to claim 11, comprising, based on 100% by mass of the catalyst: the modified NaY molecular sieve composite material comprises, by dry basis, 35-60% of clay, 20-50% of binder, and 0.1-1% of transition metal.
13. A waste plastic cracking method, characterized in that the molecular sieve catalyst for cracking waste plastic prepared according to any one of claims 1 to 10 is used in the waste plastic cracking process, the cracking conditions are a cracking temperature of 320 to 450 ℃, a pressure of 0.1 to 1.0MPa, and the mass ratio of the catalyst to the waste plastic is 2 to 15 wt%.
14. The waste plastic cracking method of claim 13, wherein the waste plastic is one or more of waste low density polyethylene, high density polyethylene, polypropylene, and polystyrene.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992113A (en) * | 2010-11-24 | 2011-03-30 | 同济大学 | Method for preparing fuel oil catalyst by lightening waste plastic pyrolysed oil and application of fuel oil catalyst |
| CN102039155A (en) * | 2010-11-25 | 2011-05-04 | 同济大学 | Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof |
| CN102133542A (en) * | 2010-01-27 | 2011-07-27 | 华东理工大学 | Compound type cracking catalyst and preparation method thereof |
| US20140228204A1 (en) * | 2013-02-12 | 2014-08-14 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products |
| CN104525243A (en) * | 2014-12-10 | 2015-04-22 | 郭帅 | Novel efficient environment-friendly catalyst for regenerating oil from waste plastic |
| CN110523431A (en) * | 2018-05-24 | 2019-12-03 | 中国石油天然气股份有限公司 | NaY molecular sieve composite material and preparation method thereof |
-
2021
- 2021-01-06 CN CN202110011768.9A patent/CN114713268B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102133542A (en) * | 2010-01-27 | 2011-07-27 | 华东理工大学 | Compound type cracking catalyst and preparation method thereof |
| CN101992113A (en) * | 2010-11-24 | 2011-03-30 | 同济大学 | Method for preparing fuel oil catalyst by lightening waste plastic pyrolysed oil and application of fuel oil catalyst |
| CN102039155A (en) * | 2010-11-25 | 2011-05-04 | 同济大学 | Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof |
| US20140228204A1 (en) * | 2013-02-12 | 2014-08-14 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products |
| CN104525243A (en) * | 2014-12-10 | 2015-04-22 | 郭帅 | Novel efficient environment-friendly catalyst for regenerating oil from waste plastic |
| CN110523431A (en) * | 2018-05-24 | 2019-12-03 | 中国石油天然气股份有限公司 | NaY molecular sieve composite material and preparation method thereof |
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