CN115069295B - Preparation method of catalyst for catalytic pyrolysis waste - Google Patents
Preparation method of catalyst for catalytic pyrolysis waste Download PDFInfo
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- CN115069295B CN115069295B CN202210840001.1A CN202210840001A CN115069295B CN 115069295 B CN115069295 B CN 115069295B CN 202210840001 A CN202210840001 A CN 202210840001A CN 115069295 B CN115069295 B CN 115069295B
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- solution
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- chloride
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- 239000002699 waste material Substances 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 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 description 9
- 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 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003546 flue gas Substances 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 5
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 5
- RPQMMLLZJBYZCY-UHFFFAOYSA-K trichlorocerium pentahydrate Chemical compound O.O.O.O.O.Cl[Ce](Cl)Cl RPQMMLLZJBYZCY-UHFFFAOYSA-K 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 3
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 2
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 2
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000010920 waste tyre Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical group [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- -1 aldamines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical class O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/204—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a catalyst for catalytic pyrolysis waste, which takes a self-made layered structure material as a base, and after being inserted into a proper acid-base active center, the catalyst can be used as a pre-cracking place and can also be used for converting SOx in flue gas into H 2 The S can promote the full combustion of CO, and mainly aims at the cracking treatment of the rubber waste containing various additives, so that the better product distribution can be obtained, the problem of disordered emission of sulfur can be avoided, and the method has better economic and social benefits.
Description
Technical Field
The invention relates to a preparation method of a catalyst for catalytic pyrolysis waste, belonging to the field of catalyst preparation.
Background
The waste rubber is one of solid wastes, and mainly comprises waste rubber products, namely scrapped tires, manual tires, rubber tubes, adhesive tapes, industrial sundries and the like, and the other part of the waste rubber products are from leftover materials and waste products generated in the production process of rubber product factories.
The disposal of waste rubber is one of the serious problems faced by people today, in order to meet the requirements of continuously improving the material performance, the rubber is developed towards high strength, wear resistance and aging resistance, and meanwhile, the problem that the waste rubber cannot be naturally degraded for a long time is also caused, and a large amount of waste rubber causes black pollution which is more difficult to dispose than plastic pollution (white pollution), and millions of tons of waste rubber are produced every year worldwide.
The waste rubber contains various additives
(1) Sulfur is taken as a main material, and the sulfur dioxide is changed into sulfur dioxide to be discharged along with flue gas to form acid rain during regeneration;
(2) And (3) supplementing a filling agent: the high proportion of carbon black is as many as 52 carbon blacks used in rubber industry, the carbon black wraps rubber particles during cracking and gasification, the carbon black is insufficient during combustion, the oxygen consumption is high, and the high temperature of regenerated coke is more demanding on the tolerance of a catalyst carrier.
(3) Anti-aging agent, physical and chemical anti-aging agent: amines, ketoamines, aldamines, phenols, and the like.
(4) Vulcanization accelerators and accelerator aids: calcium oxide, magnesium oxide, zinc oxide, stearic acid, TMTD, DM, and the like.
(5) Foaming agent: sodium bicarbonate.
(6) Coloring agent: and (3) metals.
At present, the foreign solutions mainly include two methods, namely, waste rubber burns at high temperature, high pressure and high concentration oxygen to generate heat, and the method provides supplementary energy for factories needing steam, which has the disadvantages of large investment, unsafe and high cost. Secondly, the waste rubber is ground into powder by a physical method for recycling, and the defect that only the natural rubber part can be utilized and a large amount of secondary waste is still remained.
It has also been studied abroad that the polymer rubber containing polyisoprene is subjected to thermal decomposition to break the chain into small molecular petroleum gas and fuel oil, and the decomposed waste residue is changed into carbon black product, and the carbon black product is still in the test stage.
CN107391C discloses a method for producing gasoline, diesel and carbon black from waste tyre and its equipment, said method is characterized by that after the waste tyre is broken, it is fed into thermal cracking reactor, at the same time, nitrogen gas, water vapour and combustion waste gas are introduced as carrier gas, and heated to 370-500 deg.C, and retained for 5-20 min so as to obtain gasoline, light diesel and heavy diesel.
CN1869160a discloses a method for preparing fuel oil by catalytic cracking of junked tires, which uses a cracking catalyst barium titanium ore composite oxide.
At present, thermal cracking or catalytic cracking of waste rubber becomes a research hot spot, but basically still exists in a laboratory stage, and the problems of low yield, poor selectivity and the like exist, and a proper catalyst is needed to be selected to improve a cracking product.
Disclosure of Invention
Aiming at some problems existing in the prior art, the invention aims to provide a preparation method of a waste material conversion oil catalyst.
The preparation method comprises the following steps:
(1) Preparing magnesium chloride, calcium chloride and hydrochloric acid into solution A;
(2) Adding the solution A into the sodium metaaluminate solution according to a certain proportion, uniformly stirring, heating and standing for 5-10 hours;
(3) Sequentially adding cerium chloride, vanadyl oxalate and aluminum sulfate solution into the solution in the step (2), and aging for 30 minutes;
(4) Adding ammonia water into the solution in the step (3) until the pH value is 6-8, filtering and washing;
(5) And (3) pulping a filter cake, adding ZSM-5, a Y-type molecular sieve and hydrochloric acid in a certain proportion, performing spray granulation, roasting, washing and drying to obtain the target.
In the step (1) and (2), the adding proportion of magnesium chloride, calcium chloride and sodium metaaluminate is as follows in terms of mass ratio of oxide: caO: al (Al) 2 O 3 ＝1.95-2.05：0.9-1.1：1。
The addition of hydrochloric acid in step (1) was 0.45m in terms of HCl MgO +0.1m CaO -0.4m Al2O3 。
In the step (3), the addition amount of cerium chloride is 8-15wt% of the dry basis of the title substance based on cerium oxide, the addition amount of vanadyl oxalate is 0.5-1.3wt% of the dry basis of the title substance based on vanadium pentoxide, and the addition amount of aluminum sulfate is 5-10wt% of the dry basis of the title substance based on aluminum oxide.
The ZSM-5+Y type molecular sieve in step (5) is added in an amount of 20 to 35 weight percent based on the dry basis of the title.
The addition amount of hydrochloric acid in the step (5) is (0.005-0.030) m in terms of HCl Al2O3 。
The catalyst prepared by the invention has the following remarkable advantages:
(1) The self-made magnesium-aluminum material has a layered structure, and certain intervals are arranged between the layers, so that the diffusion of oil-gas macromolecules can be realized, and the self-made magnesium-aluminum material can be used as a presplitting place.
(2) The ions between layers have exchangeable characteristics, so that proper metal ions can be inserted to realize special functions, and the cerium metal inserted by the invention has elements with oxygen storage function, can realize combustion supporting function and promote the full combustion of CO.
(3) The magnesium-aluminum structure cooperates with cerium and vanadium to convert SOx in the flue gas into H 2 S, the disordered emission of SOx is reduced, and the environment is protected.
The specific embodiment is as follows:
the present invention will be further described with reference to examples, which are only some of the examples of the present invention and are not meant to limit the scope of the present invention.
The raw materials used are all industrial grade and are obtained from Qingdao Huicheng environmental protection technology Co.Ltd.
Pulverizing waste rubber into 1-5mm particles, and collecting the waste from shoe factory.
The evaluation device is a self-built tubular reaction furnace, rubber particles are injected into the furnace after being pressurized in a glass conical feeder, the catalyst material is 5cm high, the reaction temperature is 480 ℃, and the product is subjected to condensation and collection and then is analyzed and tested by using gas chromatography.
Example 1
(1) 1436.5g of magnesium chloride hexahydrate, 279g of calcium chloride and 85.1g of hydrochloric acid were prepared into a solution A;
(2) Solution A was added to 1410ml of sodium metaaluminate (Al 2 O 3 =100 g/L), stirring uniformly, heating to 75±2 ℃, and standing for 8 hours;
(3) Adding 181.8g of cerium chloride pentahydrate, 8.52g of vanadyl oxalate and 1111ml of aluminum sulfate solution into the solution in the step (2) in sequence, and aging for 30 minutes;
(4) Adding ammonia water into the solution in the step (3) until the pH value is 7.1, filtering and washing;
(5) And (3) pulping a filter cake, adding 250g of ZSM-5 and Y-type molecular sieve and 18.5g of hydrochloric acid (13 wt%) into the filter cake, carrying out spray granulation, roasting, washing and drying, and marking as CAT-1.
Example 2
(1) 1314.7g of magnesium chloride hexahydrate, 249.5g of calcium chloride and 78.8g of hydrochloric acid were prepared into a solution A;
(2) Solution A was added to 1260ml of sodium metaaluminate (Al 2 O 3 =100 g/L) solution, stirred well, literStanding for 6 hours at 83+/-2 ℃;
(3) Adding 227.3g of cerium chloride pentahydrate, 13.6g of vanadyl oxalate and 888.9ml of aluminum sulfate solution into the solution in the step (2) in sequence, and aging for 30 minutes;
(4) Adding ammonia water into the solution in the step (3) until the pH value is 7.5, filtering and washing;
(5) And (3) pulping a filter cake, adding 300g of ZSM-5 and Y-type molecular sieve and 31.7g of hydrochloric acid (13 wt%) into the filter cake, carrying out spray granulation, roasting, washing and drying, and recording as CAT-2.
Example 3
(1) 1187.8g of magnesium chloride hexahydrate, 203.9g of calcium chloride and 68.9g of hydrochloric acid were prepared as a solution A;
(2) Solution A was added to 1140ml of sodium metaaluminate (Al 2 O 3 =100 g/L), stirring uniformly, heating to 65±2 ℃, and standing for 8 hours;
(3) 272.7g of cerium chloride pentahydrate, 17.1g of vanadyl oxalate and 777.8ml of aluminum sulfate solution are sequentially added into the solution in the step (2), and the mixture is aged for 30 minutes;
(4) Adding ammonia water into the solution in the step (3) until the pH value is 6.5, filtering and washing;
(5) And (3) pulping the filter cake, adding 350g of ZSM-5 and Y-type molecular sieve and 35.4g of hydrochloric acid (13 wt%) into the filter cake, spraying, granulating, roasting, washing and drying the mixture, and recording the mixture as CAT-4.
Example 4
(1) 1553.3g of magnesium chloride hexahydrate, 273.3g of calcium chloride and 90.3g of hydrochloric acid are prepared into a solution A;
(2) Solution A was added to 1530ml of sodium metaaluminate (Al 2 O 3 =100 g/L), stirring uniformly, heating to 80±2 ℃, and standing for 10 hours;
(3) Sequentially adding 318.2g of cerium chloride pentahydrate, 22.1g of vanadyl oxalate and 555.6ml of aluminum sulfate solution into the solution in the step (2), and aging for 30 minutes;
(4) Adding ammonia water into the solution in the step (3) until the pH value is 6.9, filtering and washing;
(5) Adding 200g of ZSM-5 and Y-type molecular sieve and 12.5 of hydrochloric acid (13 wt%) into the filter cake, granulating by spraying, roasting, washing and drying, and recording as CAT-4.
Example 5
(1) 1578.7g of magnesium chloride hexahydrate, 338.6g of calcium chloride and 94.7g of hydrochloric acid were prepared into a solution A;
(2) Solution A was added to 1560ml of sodium metaaluminate (Al 2 O 3 =100 g/L), stirring uniformly, heating to 88±2 ℃, and standing for 5 hours;
(3) Adding 227.3g of cerium chloride pentahydrate, 20.4g of vanadyl oxalate and 555.6ml of aluminum sulfate solution into the solution in the step (2) in sequence, and aging for 30 minutes;
(4) Adding ammonia water into the solution in the step (3) until the pH value is 8.7, filtering and washing;
(5) Adding 200g of ZSM-5 and Y-type molecular sieve and 47.5g of hydrochloric acid (13 wt%) into the filter cake, granulating by spraying, roasting, washing and drying, and recording as CAT-5.
The catalysts prepared in the above examples were subjected to hydrothermal aging treatment before use, and the evaluation results were as follows:
| CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | |
| dry gas, wt% | 3.87 | 3.33 | 4.01 | 3.01 | 2.45 |
| Liquefied gas, wt% | 13.68 | 11.56 | 15.12 | 12.01 | 9.82 |
| C5 gasoline, wt% | 44.97 | 45.70 | 43.85 | 46.63 | 44.94 |
| Diesel oil, wt% | 15.87 | 18.71 | 14.98 | 18.12 | 22.13 |
| Heavy oil, wt% | 3.09 | 3.89 | 2.07 | 4.00 | 5.01 |
| Coke, wt% | 18.25 | 16.81 | 19.97 | 16.23 | 15.65 |
| Light weight percent | 74.52 | 75.97 | 74.05 | 76.76 | 76.89 |
From the point of view of product distribution, the ideal light yield is obtained after treatment of the waste material with the catalyst of the invention.
Claims (1)
1. The preparation method of the catalyst for catalytic pyrolysis waste comprises the following specific preparation steps:
(1) Preparing magnesium chloride, calcium chloride and hydrochloric acid into solution A;
(2) Adding the solution A into a sodium metaaluminate solution according to a certain proportion, wherein the adding proportion of magnesium chloride, calcium chloride and sodium metaaluminate is MgO: caO: al (Al) 2 O 3 =1.95-2.05: 0.9-1.1:1, stirring uniformly, heating and standing for 5-10 hours;
(3) Sequentially adding cerium chloride, vanadyl oxalate and aluminum sulfate solution into the solution in the step (2), wherein the addition amount of the cerium chloride accounts for 8-15wt% of the dry catalyst base based on cerium oxide, the addition amount of the vanadyl oxalate accounts for 0.5-1.3wt% of the dry catalyst base based on vanadium pentoxide, the addition amount of the aluminum sulfate accounts for 5-10wt% of the dry catalyst base based on aluminum oxide, and aging for 30 minutes;
(4) Adding ammonia water into the solution in the step (3) until the pH value is 6-8, filtering and washing;
(5) Adding ZSM-5 and Y-type molecular sieve and hydrochloric acid in a certain proportion after re-pulping the filter cake, wherein the addition amount of the ZSM-5 and the Y-type molecular sieve accounts for 20-35wt% of the dry basis of the catalyst, and performing spray granulation, roasting, washing and drying to obtain the catalyst.
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| CN113976098A (en) * | 2021-11-09 | 2022-01-28 | 青岛惠城环保科技股份有限公司 | Preparation method of alkaline catalyst for thermal cracking of waste plastics |
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| CN113976098A (en) * | 2021-11-09 | 2022-01-28 | 青岛惠城环保科技股份有限公司 | Preparation method of alkaline catalyst for thermal cracking of waste plastics |
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| 废塑料在改性ZSM-5上裂解转化生产车用液体燃料;安杰;朱向学;李秀杰;王玉忠;陈福存;谢素娟;徐龙伢;;化工进展(S1);全文 * |
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