CN114425295B - Multifunctional catalytic cracking metal trapping agent and preparation method thereof - Google Patents
Multifunctional catalytic cracking metal trapping agent and preparation method thereof Download PDFInfo
- Publication number
- CN114425295B CN114425295B CN202011008423.XA CN202011008423A CN114425295B CN 114425295 B CN114425295 B CN 114425295B CN 202011008423 A CN202011008423 A CN 202011008423A CN 114425295 B CN114425295 B CN 114425295B
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- heat capacity
- matrix material
- specific heat
- high specific
- aluminum
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 178
- 239000002184 metal Substances 0.000 title claims abstract description 178
- 238000002360 preparation method Methods 0.000 title claims abstract description 97
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 167
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 106
- 239000000203 mixture Substances 0.000 claims abstract description 66
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 48
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000004927 clay Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 2
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 2
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 84
- 230000032683 aging Effects 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000003054 catalyst Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 45
- 239000011148 porous material Substances 0.000 claims description 45
- 239000002002 slurry Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 41
- 229910052782 aluminium Inorganic materials 0.000 claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052582 BN Inorganic materials 0.000 claims description 32
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 32
- 150000002696 manganese Chemical class 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- 150000001639 boron compounds Chemical class 0.000 claims description 25
- 239000004202 carbamide Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 25
- 239000012266 salt solution Substances 0.000 claims description 25
- 229910052810 boron oxide Inorganic materials 0.000 claims description 24
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 239000000084 colloidal system Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 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 13
- 229910052621 halloysite Inorganic materials 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910001437 manganese ion Inorganic materials 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 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 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- -1 rectorite Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- AETFVXHERMOZAM-UHFFFAOYSA-N B(O)(O)O.N.N Chemical compound B(O)(O)O.N.N AETFVXHERMOZAM-UHFFFAOYSA-N 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 239000011959 amorphous silica alumina Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 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 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 229940092782 bentonite Drugs 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
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims 1
- 239000010432 diamond Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 22
- 239000007787 solid Substances 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000000571 coke Substances 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- 239000001099 ammonium carbonate Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000295 fuel oil Substances 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 238000011109 contamination Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000012501 ammonium carbonate Nutrition 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004537 pulping Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 101100381981 Caenorhabditis elegans bam-2 gene Proteins 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- GZGREZWGCWVAEE-UHFFFAOYSA-N chloro-dimethyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)Cl GZGREZWGCWVAEE-UHFFFAOYSA-N 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940077478 manganese phosphate Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000004876 x-ray fluorescence 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- 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
- B01J33/00—Protection of catalysts, e.g. by coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Abstract
The invention provides a catalytic cracking multifunctional metal trapping agent and a preparation method thereof, wherein the metal trapping agent comprises 1-60 wt% of high specific heat capacity matrix material, 40-99 wt% of heat-resistant inorganic oxide and 0-50 wt% of clay; wherein the high specific heat capacity matrix material contains at least 5 wt% manganese oxide with a specific heat capacity of 1.3-2.0J/(g·k). The preparation method of the high specific heat capacity matrix material comprises the following steps: the preparation raw materials including the manganese source are formed into a mixture, and optionally subjected to washing and/or drying and/or roasting steps. The metal trapping agent provided by the invention can be used for processing hydrocarbon oil raw materials with high carbon residue value and multiple metals, can effectively trap metals in the raw materials, is environment-friendly and pollution-free in components, and has good economic benefits.
Description
Technical Field
The invention relates to a catalytic cracking multifunctional metal trapping agent and a preparation method thereof.
Background
With the increasing shortage of petroleum resources, crude oil prices are continually rising, and catalytic cracking is an important means of heavy oil processing by deep processing of heavy oils and the use of poor quality oils to reduce costs for maximum benefit.
However, the heavy metal (such as vanadium and nickel) content of inferior crude oil is generally high, and particularly in recent years, the phenomenon of metal poisoning of catalytic cracking catalysts is becoming more common due to heavy weight and poor quality of raw oil and processing of opportunity crude oil. Numerous research results show that once metals such as iron, nickel and the like are deposited on the surface, the metals are difficult to migrate, and the metals can interact with elements such as silicon, aluminum, vanadium, sodium and the like to form low-melting-point eutectic, so that the surface of the catalyst is sintered, a dense layer with the thickness of 2-3 mu m is formed on the surface, a pore canal for entering the catalyst and diffusing a product is blocked, and the product distribution is deteriorated. Serious metal contamination can lead to outstanding problems such as poor fluidization of the catalyst, reduced accessibility to active sites, poor selectivity of the catalyst, increased dry gas and coke yields, and even risk of downtime of some devices.
In order to solve the metal problems, the prior art uses a metal trapping agent to be matched with a catalytic cracking main catalyst with a catalytic cracking function so as to reduce the pollution of metal to the main catalyst. However, since the metal collector is not highly active, it tends to cause deterioration of distribution of the conversion product.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a multifunctional metal trapping agent capable of trapping polluted metals in catalytic cracking raw oil, wherein the metal trapping agent has a function of trapping various polluted metals and a catalytic function, and can also be called as the multifunctional catalytic cracking metal trapping agent. The invention aims to provide a preparation method of the multifunctional metal trapping agent.
The present invention provides a multifunctional metal trapping agent, wherein the metal trapping agent contains (a) 1 to 60% by weight of a high specific heat capacity matrix material, (b) 40 to 99% by weight of a heat-resistant inorganic oxide, and (c) 0 to 50% by weight of clay, on a dry basis, based on the total weight of the metal trapping agent; wherein the high specific heat capacity matrix material comprises at least 5 wt% manganese oxide and has a specific heat capacity of 1.3-2.0J/(g·k) at a temperature of 1000K.
According to the above technical scheme, the multifunctional metal trapping agent comprises a high specific heat capacity matrix material containing Al 2 O 3 5-95 wt.% of alumina, in MnO 2 5-95 wt.% manganese oxide and 0-40 wt.% boron compound on a dry basis.
According to any one of the technical schemes, the multifunctional metal trapping agent is characterized in that the boron compound is boron nitride and/or boron oxide.
The multifunctional metal trapping agent according to any one of the above technical solutions, wherein the specific surface area of the high specific heat capacity matrix material is 150-500m 2 ·g -1 。
The multifunctional metal trapping agent according to any one of the above-mentioned aspects, wherein the high specific heat capacity matrix material has a pore volume of 0.3 to 1.5cm 3 ·g -1 。
The multifunctional metal trapping agent according to any one of the above technical solutions, wherein the average pore diameter of the high specific heat capacity matrix material is 3-20nm.
The multifunctional metal collector according to any one of the above technical solutions, wherein the XRD pattern of the high specific heat capacity matrix material has an intensity ratio of 1 between peaks at angles 2Θ of 18±0.5° and angles 2Θ of 37±0.5°: (3-10).
According to any one of the technical schemes, the preparation method of the high specific heat capacity matrix material comprises the following steps:
(1) Mixing an aluminum source with alkali to form a colloid containing aluminum, wherein the pH value of the colloid containing aluminum is 7-11;
(2) Mixing manganese salt solution with pH value of 3-7 with urea to obtain manganese source solution;
(3) Forming a mixture of an aluminum-containing colloid, a manganese source solution, and optionally a boron compound; and optionally
(4) Washing and/or drying and/or calcining.
According to the technical scheme, in the preparation method of the high specific heat capacity matrix material, the step of mixing the aluminum source and the alkali into the gel comprises the following steps: mixing the aluminum source solution and the alkali solution to form colloid with the temperature of room temperature to 85 ℃ and the pH value of 7-11.
The multifunctional metal trapping agent according to any one of the above aspectsIn the preparation method of the high specific heat capacity matrix material, the concentration of alumina in the aluminum source solution is 150-350gAl 2 O 3 and/L, wherein the concentration of the alkali in the alkali solution is 0.1-1mol/L.
According to any one of the above technical solutions, in the preparation method of the high specific heat capacity matrix material, the aluminum source is one or more selected from aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride, and the like; the alkali is one or more of carbonate dissolved in water, bicarbonate dissolved in water and hydroxide dissolved in water.
According to any one of the above aspects, wherein, in the preparation method of the high specific heat capacity matrix material, the alkali solution is selected from the group consisting of a solution containing CO 3 2- 、HCO 3 - Or OH (OH) - An aqueous alkaline solution of one or more of the bases, CO in the alkaline solution 3 2- The concentration of (C) is 0-0.6mol/L, OH - The concentration of (C) is 0-0.5mol/L, HCO 3 - The concentration of (C) is 0-1mol/L.
According to any one of the above technical solutions, in the preparation method of the high specific heat capacity matrix material, in the step (2), the molar ratio of urea to manganese ions is 1-5, for example, 2-4, and the concentration of manganese salt in the manganese salt solution is represented by MnO 2 Can be 50-500 g.L -1 。
According to any one of the technical schemes, in the preparation method of the high specific heat capacity matrix material, urea is added into the manganese salt solution in the step (2), and then the manganese salt solution is stirred at room temperature for 30-60 minutes to obtain a manganese source solution.
According to any one of the above technical solutions, in the preparation method of the high specific heat capacity matrix material, the boron-containing compound is boron nitride and/or boron oxide precursor.
According to any one of the above technical solutions, in the preparation method of the high specific heat capacity matrix material, the boron nitride is at least one selected from hexagonal boron nitride, cubic boron nitride, rhombohedral Fang Danhua boron and wurtzite boron nitride; the boron oxide precursor is one or more of ammonium borate, ammonium hydrogen borate or boric acid.
According to any one of the technical schemes, in the preparation method of the high specific heat capacity matrix material, the step (3) further comprises an aging process after the aluminum-containing colloid and the manganese source solution are mixed, wherein the aging temperature is between room temperature and 120 ℃, the aging time is between 4 and 72 hours, and the aging is carried out under stirring or standing for aging; preferably, the aging is carried out under stirring, the aging temperature is 60-100 ℃, and the aging time is 12-36h.
According to any one of the technical schemes, wherein in the preparation method of the high specific heat capacity matrix material, the boron compound is boron nitride; the method for forming the mixture of the aluminum-containing colloid, the manganese source solution and the boron compound in the step (3) is as follows: mixing an aluminum-containing colloid, a manganese source solution and a boron compound, and aging.
According to any one of the above technical solutions, in the preparation method of the high specific heat capacity matrix material, the boron compound is boron oxide and/or a precursor of boron oxide, and the method for forming a mixture of the aluminum-containing colloid, the manganese source solution and the boron compound in the step (3) is as follows: mixing an aluminum-containing colloid, a manganese source solution, aging, optionally washing, and then mixing with a boron compound.
According to any one of the above technical solutions, in the preparation method of the high specific heat capacity matrix material, the baking temperature in the step (4) may be 500 ℃ to 900 ℃ and the baking time may be 4 hours to 8 hours.
The invention also provides a preparation method of the multifunctional metal trapping agent, which comprises the following steps: a slurry is formed comprising the high specific heat capacity matrix material, the refractory inorganic oxide and/or refractory inorganic oxide precursor, water and optionally clay, the slurry being referred to as a first slurry, and the steps of drying and firing.
According to one embodiment of the method for preparing the multifunctional metal trapping agent provided by the invention, an acid is further added into the first slurry, wherein the acid can be one or more selected from inorganic acid and organic acid which are soluble in water, such as one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid and acetic acid.
According to the preparation method of the multifunctional metal trapping agent, provided by the invention, the process of forming the first slurry further comprises the step of aging. The aging is performed after the addition of the acid, and in one mode, the aging temperature of the aging is 20-60 ℃ and the aging time is 0.1-5 hours.
According to the preparation method of the multifunctional metal trapping agent, in the process of forming the first slurry, at least part of high specific heat capacity matrix material is added before aging, preferably, the high specific heat capacity matrix material is added in two parts, wherein one part is added before aging and is called a first high specific heat capacity matrix material, and the other part is added after aging and is called a second high specific heat capacity matrix material. In one embodiment, the first high specific heat capacity matrix material, the refractory inorganic oxide and/or refractory inorganic oxide precursor, water, acid, and optionally clay are mixed to form a second slurry having a pH of 1-5, aged, optionally with the addition of a second high specific heat capacity matrix material; preferably, the aging is carried out at a temperature of 20-60 ℃ for 0.1-5 hours; the acid may be selected from one or more of inorganic and organic acids soluble in water, such as one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid. Preferably, the weight ratio of the first high specific heat capacity matrix material to the second high specific heat capacity matrix material is 1: (0.1-6) is preferably 1: (0.1-3)
In the preparation method of the multifunctional metal trapping agent provided by the invention, the first slurry contains heat-resistant inorganic oxide and/or a precursor of the heat-resistant inorganic oxide. The refractory inorganic oxide is, for example, alumina, silica-alumina. The precursor of the refractory inorganic oxide refers to one or more substances capable of forming the refractory inorganic oxide during the preparation of the metal collector. The precursor of alumina may be selected from hydrated alumina and/or alumina sol; the hydrated alumina is selected from one or more of boehmite (boehmite), pseudo-boehmite (pseudo-boehmite), alumina trihydrate and amorphous aluminum hydroxide. The precursor of silicon oxide can be one or more selected from silica sol, silica gel and water glass. The precursor of amorphous silica-alumina may be one or more selected from silica-alumina sol, mixture of silica-sol and alumina sol, and silica-alumina gel.
The multifunctional metal trapping agent provided by the invention has at least one of the following beneficial effects, and preferably has various or all of the beneficial effects:
(1) Can capture metal pollutants such as vanadium, iron, calcium, nickel and the like in oil products;
(2) The method is favorable for the entry and adsorption of heavy metal chelates and colloid molecules in poor raw materials, and has better metal trapping effect;
(3) The metal trapping catalyst provided by the invention can effectively adsorb carbon residue of inferior raw materials;
(4) The catalyst is used by being mixed with a catalytic cracking main catalyst, so that the main catalyst can be effectively protected, and the catalytic cracking effect is better improved.
(5) Has better catalytic capability, is used for heavy oil conversion, and can increase the gasoline yield and/or improve the heavy oil conversion rate and/or reduce the coke yield.
(6) In the case of metal contamination, it is possible to increase the gasoline yield and/or to increase the heavy oil conversion and/or to decrease the coke yield.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The multifunctional metal trapping agent (called metal trapping agent for short) provided by the invention contains a high specific heat capacity matrix material, and contains or does not contain heat-resistant inorganic oxide and contains or does not contain clay, wherein the content of the high specific heat capacity matrix material is 1-60 wt%, the content of the heat-resistant inorganic oxide is 40-99 wt% and the content of the clay is 0-50 wt% based on the total weight of the metal trapping agent. Preferably, the high specific heat capacity matrix material is present in an amount of 5 to 50 wt%, the refractory inorganic oxide is present in an amount of 40 to 70 wt%, and the clay is present in an amount of 0 to 40 wt%.
In the metal trapping agent provided by the invention, the heat-resistant inorganic oxide may be selected from one or more of heat-resistant inorganic oxides used as a metal trapping agent matrix and a binder component, for example, one or more of alumina, silica and amorphous silica-alumina. The clay is one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. Among them, one or a mixture of several of kaolin, halloysite and montmorillonite is preferable.
In the metal trapping agent according to the first embodiment, the high specific heat capacity matrix material contains no boron compound, and the high specific heat capacity matrix material contains, based on the weight of the high specific heat capacity matrix material, al 2 O 3 5-95 wt.% of aluminium oxide and MnO 2 5-95 wt.% manganese oxide, for example, said high specific heat capacity matrix material consists essentially of 15-70 wt.% or 20-65 wt.% or 30-61 wt.% manganese oxide and 30-85 wt.% or 35-80 wt.% or 39-70 wt.% alumina. The specific surface area of the high specific heat capacity matrix material can be 180-300m 2 ·g -1 For example 200-250m 2 ·g -1 Or 220-245m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The high specific heat capacity matrix material has a pore volume of 0.35-0.75, e.g. 0.4-0.65cm 3 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The high specific heat capacity matrix material has an average pore diameter of 5-13nm, e.g. 6-11nm.
In the metal trapping agent provided by the invention, the high specific heat capacity matrix material can contain or not contain a boron compound. Preferably, the high specific heat capacity matrix material (abbreviated as the matrix material) provided by the invention contains the boron compound, and can have better wear resistance compared with the high specific heat capacity matrix material without the boron compound.
The second embodiment of the metal trapping agent provided by the inventionIn the high specific heat capacity matrix material, the boron compound is boron nitride, and the specific heat capacity is 1.3-2.0J/(g.K), for example, 1.35-1.95J/(g.K) or 1.51-1.95J/(g.K). The anhydrous chemical expression of the high specific heat capacity matrix material in weight ratio can be expressed as (5-94.5) Al 2 O 3 ·(5-94.5)MnO 2 (0.5-40) BN, which may be, for example, (20-80) Al 2 O 3 ·(15-75)MnO 2 (5-30) BN. Preferably, the high specific heat capacity matrix material contains 5 to 94.5 wt.% alumina, based on the weight of the high specific heat capacity matrix material, as MnO 2 5-94.5% by weight manganese oxide and more than 0 and not more than 40% by weight, for example 0.5-35% by weight boron nitride on a dry basis; more preferably, the high specific heat capacity matrix material contains 15 to 80 wt% alumina, 15 to 70 wt% manganese oxide and 5 to 30 wt% boron nitride; more preferably, the high specific heat capacity matrix material comprises 19-74 wt% alumina, 14-66 wt% manganese oxide and 8-26 wt% boron nitride. The high specific heat capacity matrix material contains boron nitride, so that the wear resistance can be greatly improved.
According to the second embodiment of the metal trapping agent provided by the invention, the specific surface area of the high specific heat capacity matrix material is 150-350m 2 ·g -1 For example 180-300m 2 ·g -1 Or 220-245m 2 ·g -1 Or 200-250m 2 ·g -1 The high specific heat capacity matrix material has a pore volume of 0.35-0.75, such as 0.4-0.65cm 3 ·g -1 Or 0.5-0.7cm 3 ·g -1 Or 0.45-0.75, the high specific heat capacity matrix material having an average pore diameter of 3-20nm, for example 4-18nm or 6-13nm or 5-15nm or 6-8.5nm, preferably 5-13nm or 6-11nm.
According to the metal trapping agent provided by the invention, in the case of the second embodiment, the preparation method of the high specific heat capacity matrix material comprises the following steps:
(1) Mixing an aluminum source solution and an alkali solution at room temperature to 85 ℃ to form glue, and controlling the pH value of the glue formed by the glue to be 7-11;
(2) Preparing a manganese salt solution with the pH value of 3-7, mixing the manganese salt solution with urea, and stirring; the molar ratio of urea to manganese ions is 1-5, the mixing temperature of the manganese salt solution and urea is not particularly required, the mixing is carried out at room temperature, and the stirring time is 30-60 minutes;
(3) Mixing the product obtained in the step (1), the product obtained in the step (2) and boron nitride, and aging for 4-72 hours at the temperature of room temperature to 120 ℃; and optionally, a second set of the components,
(4) Washing the product obtained in step (3) with water, preferably, the washing is performed to make the washed washing liquid neutral, wherein neutral refers to a pH value of 6.5-7.5, for example, deionized water is used for washing until the washed deionized water is neutral, and drying and roasting are performed to obtain the high specific heat capacity matrix material.
According to the metal trapping agent provided by the invention, in the second embodiment, in the preparation method of the high specific heat capacity matrix material, preferably, the alkali solution in the step (1) is a solution containing CO 3 2- 、HCO 3 2- And OH (OH) - More preferably, the alkaline aqueous solution is an aqueous solution comprising one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide, or a mixed solution of one or more of ammonium carbonate, sodium hydroxide and potassium hydroxide and ammonia water. Preferably, the total concentration of alkali in the alkali solution is 0.1-1mol/L. In one embodiment, the aqueous alkali is CO 3 2- The concentration of (C) is 0-0.6mol/L, for example 0.3-0.5mol/L; OH (OH) - The concentration of (C) is 0-0.5mol/L, for example 0.2-0.35mol/L, HCO 3 2- The concentration of (C) is 0 to 1.0mol/L, for example, 0.4 to 1.0mol/L. The pH of the gel formed in step (1) is preferably from 8 to 11, for example from 8.5 to 11 or from 9 to 10. When the ammonia water is selected, the addition amount of the ammonia water is calculated according to the calculated hydroxide radical assuming that the ammonia water is fully ionized.
According to the metal trapping agent provided by the invention, in the second embodiment, in the preparation method of the high specific heat capacity matrix material, a water-soluble aluminum source capable of being dissolved in water can be used in the invention, for example, the aluminum source can be one or more selected from aluminum nitrate, aluminum sulfate and aluminum chloride.
According to the metal trapping agent provided by the invention, in the second embodiment, in the preparation method of the high specific heat capacity matrix material, in the step (2), a manganese salt solution with a specific pH value is mixed with urea to form a mixture, and the pH value of the manganese salt solution is 3-7, preferably 5-7. In one embodiment, the method of mixing in step (2) comprises: urea is added to the manganese salt solution and stirred at room temperature for 40-60 minutes, the molar ratio of urea to manganese ions preferably being between 2 and 4. The manganese salt solution in step (2) may be selected from an aqueous solution of a water-soluble manganese salt and/or a salt solution formed after contacting a manganese oxide, a manganese hydroxide and an acid. The types of the manganese salts are wide in optional range, and water-soluble manganese salts capable of being dissolved in water, such as one or more of manganese nitrate, manganese sulfate, manganese chloride, or the like, may be used in the present invention. Manganese salt solutions may also be prepared from manganese oxides such as one or more of manganese monoxide, manganomanganic oxide, manganous oxide, manganese dioxide and/or manganese hydroxide in contact with acids such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, preferably one or more of hydrochloric acid, sulfuric acid and nitric acid.
According to the metal trapping agent provided by the invention, in the second embodiment, in the preparation method of the high specific heat capacity matrix material, the product obtained in the step (1) in the step (3) is prepared by using Al 2 O 3 Counting the product obtained in the step (2) by MnO 2 The weight proportion of boron nitride and the boron nitride is (5-95) Al 2 O 3 ：(5-95)MnO 2 : (0.5-40) BN is, for example, (20-80) Al 2 O 3 ：(15-75)MnO 2 : (5-30) BN. Preferably, the product of step (1) in step (3), the product of step (2) and the boron nitride are used in amounts such that the high specific heat capacity matrix material prepared contains 5 to 94.5 wt.% alumina, e.g. 15 to 80 wt.% or 19 to 74 wt.% or 20 to 80 wt.% or 19 to 60 wt.%, as MnO 2 5 to 94.5% by weight, for example 15 to 75% by weight or 10 to 70% by weight or 14 to 66% by weight or 19 to 66% by weight of manganese oxide and not more than 40% by weight, for example 0.5 to 35% by weight or 5 to 30% by weight or 8 to 26% by weight, of boron nitride on a dry basis.
According to the metal trapping agent provided by the invention, in the second embodiment, in the preparation method of the high specific heat capacity matrix material, the optional range of the aging condition in the step (3) is wider, and preferably, the aging condition in the step (3) includes: the aging temperature is 60-100 ℃, the aging time is 12-36h, and the mixture is aged under stirring. There is no particular requirement on the manner of stirring, and the stirring speed may be 50 to 300 rpm, for example.
According to the metal trapping agent provided by the invention, in the case of the second embodiment, in the preparation method of the high specific heat capacity matrix material, the boron nitride may be one or more selected from hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral Fang Danhua boron (r-BN) and wurtzite boron nitride (w-BN).
According to the metal trapping agent provided by the invention, in the second embodiment, in the preparation method of the high specific heat capacity matrix material, the optional range of the drying condition and the roasting condition in the step (4) is wider. The drying and roasting methods can be carried out according to the prior art. For example, the drying conditions in step (4) include: drying at 100-150deg.C for 6-24 hr; the firing conditions in step (4) include: roasting at 550-800 deg.c, e.g. 550-750 deg.c, for 4-8 hr.
According to the third embodiment of the metal trapping agent provided by the invention, the high specific heat capacity matrix material contains a boron compound, the boron compound is boron oxide, the specific heat capacity is 1.3-2.0J/(g.K), for example, 1.35-1.95J/(g.K) or 1.51-1.95J/(g.K), and the anhydrous compound composition expression of the high specific heat capacity mesoporous matrix material provided by the invention is calculated as (5-94.5) Al in terms of oxide weight ratio 2 O 3 ·(5-94.5)MnO 2 ·(0.5-10)B 2 O 3 For example (20-80) Al 2 O 3 ·(15-75)MnO 2 ·(0.5-10)B 2 O 3 Preferably (20-80) Al 2 O 3 ·(15-75)MnO 2 ·(1-8)B 2 O 3 。
According to the metal trapping agent provided by the invention, in a preferred case, the third embodiment is based on the weight of the high specific heat capacity matrix material, the high specific heat capacity matrixThe material contains MnO 2 5 to 94.5% by weight of manganese oxide, 5 to 94.5% by weight of aluminum oxide, and B 2 O 3 0.5-10 wt% boron oxide; more preferably, the high specific heat capacity matrix material contains 15 to 80 wt.% alumina in MnO 2 15-80 wt% manganese oxide and B 2 O 3 0.8 to 8% by weight of boron oxide, for example, the high specific heat capacity matrix material contains 20 to 62% by weight of aluminum oxide in MnO 2 34-72 wt% manganese oxide and B 2 O 3 2 to 8% by weight of boron oxide. Preferably, the high specific heat capacity matrix material has a specific surface area of 300-500m 2 /g, e.g. 310-370m 2 /g or 330-370m 2 Per g, pore volume of 0.5-1.5cm 3 Per gram, for example, 0.7-1.4cm 3 /g or 0.7-1.2cm 3 /g or 0.6-1.3cm 3 And/g. Preferably, the matrix material is a mesoporous matrix material having an average pore size of 3-20nm, e.g. 5-18nm or 7-15nm or 8-18nm or 8-14nm or 10-15nm or 10-13nm.
According to the metal trapping agent provided by the invention, in the third embodiment, the boron compound contained in the high specific heat capacity matrix material is boron oxide, so that the boron oxide has higher pore volume and specific surface area, and the boron oxide is introduced, so that the acidity is modulated, the pre-cracking capability of the metal trapping agent is improved, besides the metal can be trapped, the metal trapping agent can be applied to heavy oil catalytic cracking, the particle temperature of a catalytic cracking catalyst during regeneration can be reduced, the collapse of a molecular sieve is slowed down, the activity, the metal pollution resistance and the heavy oil conversion capability of the catalyst are improved, the coke selectivity of the catalyst is reduced, and the fluidization performance of the catalyst is good.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, the preparation method of the high specific heat capacity matrix material comprises the following steps:
(1) Mixing an aluminum source solution and an alkali solution at room temperature to 85 ℃ to form a gel, and controlling the pH value of the gel obtained by the gel forming to be 7-11;
(2) Preparing a manganese salt solution with the pH value of 3-7, mixing the manganese salt solution with urea, and stirring for 30-60 minutes at room temperature; wherein the molar ratio of urea to manganese ions is 1-5;
(3) Mixing the product obtained in the step (1) with the product obtained in the step (2), and aging; the aging is for example at room temperature to 120 ℃ for 4-72 hours; mixing the aged solid product with a boron oxide source or mixing the aged solid product after washing with the boron oxide source, and optionally carrying out a reaction; wherein in B 2 O 3 The weight ratio of the calculated boron oxide source feeding amount to the high specific heat capacity matrix material calculated on a dry basis is (0.005-0.1): 1, a step of;
(4) Directly drying and roasting the solid precipitate (or called solid product) obtained in the step (3), or washing, drying and roasting the solid precipitate obtained in the step (3); the solid product of step (3) may be washed with water, for example, by washing with water to neutrality.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, compared with the matrix material with high specific heat capacity obtained by other methods, the matrix material prepared by the preparation method of the matrix material with high specific heat capacity has higher specific heat capacity, can also have higher average pore diameter, can have higher specific surface area and higher pore volume, can have higher liquid product yield when being used for heavy oil catalytic cracking with high metal content, particularly high iron content, and has lower dry gas and coke yield.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, in the preparation method of the high specific heat capacity matrix material, the optional range of the alkaline solution in the step (1) is wider, and preferably, the alkaline solution in the step (1) contains HCO 3 2- 、CO 3 2- And OH (OH) - Preferably, the alkaline aqueous solution comprises one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide, or comprises a mixed solution of one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide and ammonia water. Preferably, the total concentration of alkali in the alkali solution is 0.1-1mol/L. Preferably, in the alkali solution, CO 3 2- At a concentration of 0 to 0.6mol/L, for example 0.3-0.5mol/L；OH - The concentration of (C) is preferably 0 to 0.5mol/L, for example 0.2 to 0.35mol/L, HCO 3 2- The concentration of (C) is 0 to 1.0mol/L, for example, 0.4 to 1.0mol/L. When the ammonia water is selected, the addition amount of the ammonia water is calculated according to the calculated hydroxide radical assuming that the ammonia water is fully ionized. The pH of the colloid obtained by the colloid formation is preferably 9-11 or 10-11.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, in the preparation method of the high specific heat capacity matrix material, the aluminum source may be a water-soluble aluminum source capable of being dissolved in water, for example, the soluble aluminum source may be selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride and the like, and preferably one or more of aluminum nitrate, aluminum sulfate, aluminum chloride and the like.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, in the preparation method of the high specific heat capacity matrix material, the manganese salt solution in the step (2) may be selected from an aqueous solution of water-soluble manganese salt and/or a salt solution formed after manganese oxide and manganese hydroxide are contacted with acid; the pH of the manganese salt solution is 3-7, preferably 5-7. Preferably, in step (2), after mixing the manganese salt solution with urea, stirring at room temperature for 40-60 minutes, the molar ratio of urea to manganese ions being between 2 and 4. The manganese salt solution in step (2) may be selected from an aqueous solution of a water-soluble manganese salt and/or a salt solution formed after contacting a manganese oxide, a manganese hydroxide and an acid. The types of the manganese salts may be widely selected, and water-soluble manganese salts capable of being dissolved in water, such as one or more of manganese nitrate, manganese phosphate, manganese sulfate, manganese chloride, or the like, may be used in the present invention. The manganese salt solution may also be prepared from manganese oxides such as one or more of manganese monoxide, manganomanganic oxide, manganous oxide, manganese dioxide and/or manganese hydroxide in contact with acids such as one or more of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid, preferably one or more of sulfuric acid, hydrochloric acid and nitric acid.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, the preparation method of the high specific heat capacity matrix material, and the optional aging conditions in the step (3)The range is broad, preferably, the aging conditions in step (3) include: the aging temperature is 60-100 ℃, and the stirring aging time is 12-36h. The stirring method is the existing method, for example, the stirring speed is 50-300 rpm. Filtering the aged product or washing the aged product after filtering to obtain an aged solid product. In one embodiment, the washing is performed as an aged solid product (dry basis): h 2 O=1: (5-30) contacting the aged solid product (also called precipitate) obtained by aging with water at room temperature for 0.5-1 hr for 1-3 times until the washing liquid after washing is neutral and has pH of 6.5-7.5.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, the preparation method of the high specific heat capacity matrix material is characterized in that the aged solid product is contacted with the boron source, and the contact treatment method can be various. The aged product can be filtered to obtain a filter cake, namely the aged solid product is directly mixed with a boron source, or the aged solid product obtained after the filter cake obtained by filtering is washed is mixed with the boron source; preferably, the mixture formed is also subjected to a reaction for a period of time, for example stirring or standing at room temperature to 90 ℃ for 0.2-5 hours. In one embodiment, the aged solid product is slurried with water, wherein the aged solid product (on a dry basis): h 2 The weight ratio of O is 1: (5-20), adding boron source into the slurry, standing or stirring at room temperature to 90 ℃ for 0.2-5 hours, preferably 0.5-3 hours, and filtering to obtain solid precipitate. Or mixing the aged solid product or the aged solid product after washing with a boron source in proportion, and grinding uniformly to obtain a solid precipitate.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, in the preparation method of the high specific heat capacity matrix material, the boron oxide source is preferably a substance capable of obtaining boron oxide after roasting, and for example, the substance can be one or more of ammonium borate, ammonium hydrogen borate or boric acid.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, the high specific heat capacity matrix material preparation method, the product obtained in the step (1) in the step (3) is prepared by using Al 2 O 3 Counting, obtaining in step (2)The product is MnO 2 Meter and boron source to B 2 O 3 The weight and the dosage ratio of the aluminum alloy to the aluminum alloy are (5-94.5) Al 2 O 3 ：(5-94.5)MnO 2 ：(0.5-10)B 2 O 3 Preferably (20-80) Al 2 O 3 ：(15-75)MnO 2 ：(1-8)B 2 O 3 . Preferably, the resulting high specific heat capacity matrix material comprises 5 to 94.5 wt.%, for example 15 to 80 wt.% or 30 to 72 wt.% or 22 to 72 wt.% of the high specific heat capacity matrix material as MnO 2 Manganese oxide, 5-94.5% by weight, for example 15-80% by weight or 20-62% by weight or 20-75% by weight of aluminum oxide and 0.5-10% by weight or 2-8% by weight or 0.8-8% by weight of B 2 O 3 Boron oxide.
According to the metal trapping agent provided by the invention, in the case of the third embodiment, in the preparation method of the high specific heat capacity matrix material, in the step (4), the solid precipitate obtained in the step (3) is directly dried and roasted, or is dried and roasted after being washed. Wherein the washing may be with water, for example after mixing with water, or with water, typically the solid precipitate after washing is neutral, i.e. the pH of the water after contact with water is 6.5-7.5. Wherein, the drying and roasting methods can be carried out according to the prior art. For example, the drying may be at 100-150 ℃ for 12-24 hours; the calcination may be performed at 550-800 c, for example 550-750 c, for 4-8h.
According to the preparation method of the multifunctional metal trapping agent, a high-specific-heat-capacity matrix material, a heat-resistant inorganic oxide and/or a heat-resistant inorganic oxide precursor, water and optional clay are mixed to form a slurry, and the slurry is called as a first slurry, and then dried and roasted. One embodiment comprises mixing all or part of the high specific heat capacity matrix material with water, pulping, adding or not adding clay, adding heat-resistant inorganic oxide, drying to obtain slurry, and roasting, wherein before or after adding the high specific heat capacity matrix material, adding an acid to make the pH value of the slurry obtained after adding the acid be 1-5, preferably 1.5-4, and then aging at 20-60 ℃ for 0.1-5 hours; after aging, the remaining high specific heat capacity matrix material is added. In one embodiment, the refractory inorganic oxide and/or refractory inorganic oxide precursor is added prior to the addition of the acid and the high specific heat capacity matrix material is added after the addition of the acid.
According to the preparation method of the multifunctional metal trapping agent provided by the invention, the preparation method preferably comprises the step of aging. Before aging, the high specific heat capacity matrix material may be added completely or partially, and in order to make the metal trapping agent have better wear resistance, it is preferable to add a part of the high specific heat capacity matrix material and/or its precursor before aging, and then add the rest of the high specific heat capacity matrix material and/or its precursor after aging, where the weight ratio of the part added first to the part added later is 1: (0.1-6) preferably 1: (0.1-3). The aging temperature is 20-60deg.C, preferably 20-50deg.C, and the aging time is 0.1-5 hr, preferably 0.5-4 hr.
In the preparation method of the multifunctional metal trapping agent, clay can be added into the first slurry, and the clay can be added before or after aging.
In the preparation method of the multifunctional metal trapping agent, before or after adding the high specific heat capacity matrix material, an acid is also added to enable the pH value of slurry to be 1-5, and then the slurry is aged at the temperature of 20-60 ℃ for 0.1-5 hours. The acid is one or more selected from inorganic acid and organic acid which can be dissolved in water, preferably one or more selected from hydrochloric acid, nitric acid, phosphoric acid and carboxylic acid with 1-10 carbon atoms. The acid is used in an amount to give a pH of the slurry of 1 to 5, preferably 1.5 to 4.
In the preparation method of the multifunctional metal trapping agent, the usage amount of each component is that the final metal trapping agent contains 1-60 wt% of high specific heat capacity matrix material, 40-99 wt% of heat-resistant inorganic oxide and 0-50 wt% of clay based on the total amount of the metal trapping agent. Preferably, the components are used in amounts such that the final metal trap contains 5 to 50 wt% of the high specific heat capacity matrix material, 40 to 70 wt% of the refractory inorganic oxide, and 0 to 40 wt% of the clay, based on the total amount of the metal trap.
In the method for preparing the multifunctional metal trapping agent provided by the invention, the drying method and conditions of the first slurry are well known to those skilled in the art, and for example, the drying method can be air drying, forced air drying or spray drying, and preferably spray drying. The temperature of drying may be from room temperature to 400 ℃, preferably 100-350 ℃. In order to facilitate spray drying, the solids content of the slurry before drying is preferably 10 to 50% by weight, more preferably 20 to 50% by weight.
In the preparation method of the metal trapping agent provided by the invention, the first slurry can further comprise a roasting step after being dried. In general, the firing temperature of the slurry after drying is 400 to 700 ℃, preferably 450 to 650 ℃, and the firing time is 0.5 hours or more, preferably 0.5 to 100 hours, more preferably 0.5 to 10 hours.
The metal trapping agent provided by the invention is suitable for raw materials with carbon residue value higher than 5 wt%, V content higher than 5ppm, ni content higher than 10ppm, fe content higher than 10ppm and Ca content higher than 10ppm, and the multifunctional metal trapping agent provided by the invention can be used by being mixed with a main metal trapping agent, so that metals such as nickel, vanadium, iron and the like in the raw materials can be effectively trapped, the active center of the main metal trapping agent is well protected, and the composition and the preparation method are environment-friendly and pollution-free, and have better economic benefits.
The present invention will be described in detail by examples.
The following raw materials used in the following preparation examples, comparative preparation examples, examples and comparative examples were as follows:
hydrochloric acid is produced by Beijing chemical plant, and has chemical purity and concentration of 36 wt%;
sodium water glass is commercially available, siO 2 A concentration of 26.0 wt% and a modulus of 3.2;
the halloysite is an industrial product of Suzhou porcelain clay company, and has a solid content of 71.6 weight percent;
pseudo-boehmite is a product of Shandong aluminum Co., ltd, and has a solid content of 62.0 wt%;
the alumina sol is a product of Qilu division company of China petrochemical catalyst, al 2 O 3 The content was 21.5 wt%;
industrial catalytic cracking catalysts are supplied by the zilu catalyst plant under the designation CDOS, hereinafter referred to as catalyst C.
The invention is further illustrated by the following examples, which are not intended to limit the same.
In the present invention, the catalyst to oil ratio refers to the mass ratio of the catalyst to the raw oil.
In the present invention, ppm is ppm by weight unless otherwise specified.
And BN used is hexagonal boron nitride.
In each of the examples and comparative examples, al in the sample 2 O 3 、MnO 2 The content of B, N, fe was measured by X-ray fluorescence (see "petrochemical analysis method (RIPP Experimental method)", yang Cuiding et al, scientific Press, 1990). The sample phase was determined by X-ray diffraction. The specific surface area, pore volume and average pore diameter of the sample are measured by a low-temperature nitrogen adsorption-desorption method and calculated by a BJH method to obtain the pore diameter distribution.
Preparation example 1
This example illustrates the preparation of a high specific heat capacity matrix material.
Concentration of 300gAl 2 O 3 Al of/L 2 (SO 4 ) 3 Solution and CO 3 2- Ammonium carbonate solution at a concentration of 0.10mol/L was mixed at 20 ℃ to form a gel, and the resulting gel had a ph=7.5, to give slurry a. To a concentration of 450gMnO 2 MnCl of/L 2 Hydrochloric acid was added to the solution, the ph=3.5 was controlled, and then urea was added to the solution in a molar ratio of urea to manganese ion of 2, and stirred at room temperature for 30 minutes to obtain solution B. Adding the solution B into the slurry A, stirring and ageing for 4 hours at 80 ℃, cooling the system to room temperature, flushing with deionized water until the washed water is neutral, drying at 120 ℃ for 12 hours to obtain a matrix material precursor, roasting at 550 ℃ for 6 hours, and cooling to room temperature along with a furnace to obtain the matrix material with high specific heat capacity, which is recorded as AM-1. The proportion of AM-1, the parameters of the preparation conditions, the specific heat capacity, the specific surface area, the pore volume and the average pore diameter are listed in Table 1.
X-ray of AM-1The line diffraction patterns have diffraction peaks at angles of 2 theta of 18 + -0.5 DEG, 37 + -0.5 DEG, 48 + -0.5 DEG, 59 + -0.5 DEG and 66 + -0.5 deg. Wherein the intensity ratio (I1/I2) of the peak at an angle of 2 theta of 18 + -0.5 DEG and an angle of 2 theta of 37 + -0.5 DEG is 1:5.2; the elemental analysis chemical composition expression (by weight) is 60.5MnO 2 ·39.5Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Specific heat capacity 1.36J/(g.K), specific surface area 238m 2 Per g, pore volume 0.38cm 3 And/g, average pore size 6.4nm.
PREPARATION EXAMPLES 2 to 4
High specific heat capacity matrix materials AM-2 to AM-4 were prepared according to the method of preparation example 1, except that the raw material ratios, preparation condition parameters, elemental composition of the product, specific heat capacity, specific surface area, pore volume and average pore diameter were as shown in table 1, wherein solution B was added to slurry a, followed by adding boron nitride, and then the aging was performed.
Preparation example 5
Preparation example 5 is used to illustrate the preparation process of the high specific heat capacity matrix material provided by the invention.
Will have a concentration of 350gAl 2 O 3 Al (NO) 3 ) 3 Solution and CO 3 2- At a concentration of 0.1mol/L (ammonium carbonate), OH - The solution with the concentration of 0.1mol/L (ammonia water) is mixed into gel at the temperature of 25 ℃ and the pH value is controlled to be 10.5, so as to obtain slurry A. Mn is added to 3 O 4 Mixing with hydrochloric acid and water to obtain 116.5gMnO 2 And (3) controlling the pH value of the manganese chloride solution to be=6, adding urea into the solution, wherein the molar ratio of the urea to manganese ions is 3, and stirring the solution at room temperature for 40 minutes to obtain solution B. Adding the solution B and 145.6gBN (with the solid content of 80 weight percent) into the slurry A, stirring and ageing for 24 hours at the temperature of 60 ℃, cooling the system to the room temperature, flushing with deionized water until the water after washing is neutral, drying for 12 hours at the temperature of 120 ℃ to obtain a matrix material precursor, roasting for 4 hours at the temperature of 650 ℃, and cooling to the room temperature along with a furnace to obtain the matrix material with high specific heat capacity, which is recorded as AM-5. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore size of AM-5 are listed in Table 1.
The X-ray diffraction pattern of AM-5 was the same as in example 1, with characteristic peaks at angles of 18.+ -. 0.5 ℃ and 37.+ -. 0.5 ℃ for 2. Theta. And bothThe intensity ratio is 1:6.6; AM-5 has a chemical composition of 20.6MnO by weight 2 ·59.4Al 2 O 3 19.4BN; specific heat capacity 1.48J/(g.K), specific surface area 243m 2 Per g, pore volume 0.46cm 3 And/g, average pore size 7.6nm.
Preparation example 6
Preparation example 6 is used to illustrate the preparation process of the high specific heat capacity matrix material provided by the present invention.
The matrix material AM-6 was prepared according to the method of preparation example 5, the composition, specific heat capacity, specific surface area, pore volume and average pore size of which are shown in Table 1, with different raw material ratios, preparation condition parameters, in which CO in an alkali solution for gel formation 3 2- The concentration is 0.2mol/L, OH - The concentration was 0.15mol/L.
The X-ray diffraction patterns of AM-2 to AM-6 were identical to the X-ray diffraction pattern of example 1, and had peaks at a 2-theta angle of 18.+ -. 0.5 DEG and a 2-theta angle of 37.+ -. 0.5 deg.
Comparative preparation example 1
Preparing deionized water with concentration of 350gAl 2 O 3 Al (NO) 3 ) 3 Solution and concentration of 525gMnO 2 And (3) uniformly mixing the manganese nitrate solution/L to obtain a solution A. An ammonium bicarbonate solution was prepared and ph=10.0 was controlled and noted as solution B. And mixing the solution A and the solution B under continuous stirring to obtain a mother solution C, and controlling the PH of the mother solution C to be 8-9 by controlling the adding amount of the solution B in the mixing process. Aging at 180deg.C for 20 hr after mixing, cooling to room temperature, washing with deionized water to neutrality, drying at 120deg.C for 12 hr to obtain manganese aluminum matrix precursor, roasting at 1000deg.C for 4 hr, cooling to room temperature with furnace to obtain contrast matrix material, and recording as DAM-1.
X-ray diffraction pattern of DAM-1, wherein the characteristic peak is present at an angle of 18±0.5° and an angle of 37±0.5° for 2θ, the intensity ratio of the two is 1:1.9; DB-1 elemental analysis chemical composition expression of 60.6MnO 2 ·39.4Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Specific heat capacity 0.62J/(g.K), specific surface area 224m 2 Per g, pore volume 0.31cm 3 And/g, average pore size 5.5nm.
Comparative preparation example 2
Will have a concentration of 350gAl 2 O 3 Al of/L 2 (SO 4 ) 3 The solution was mixed with ammonium carbonate to form a gel, and ph=10.0 was controlled to give slurry a. 209.7gMnO concentration 2 MnSO of/L 4 The solution was added to slurry A and stirred at room temperature for 30 minutes to give slurry B. Adding solution B and 95.4g of boron nitride (with the solid content of 80 weight percent) into slurry A, aging for 24 hours at the temperature of 80 ℃, cooling the system to room temperature, flushing with deionized water to neutrality, drying for 12 hours at the temperature of 120 ℃ to obtain a manganese-aluminum matrix precursor, roasting for 6 hours at the temperature of 900 ℃, and cooling to the room temperature along with a furnace to obtain a sample of the contrast matrix material, which is marked as DAM-2.
Elemental analysis (by weight) of DAM-2 with a chemical composition of 33.3MnO 2 ·54.7Al 2 O 3 11.7BN; specific heat capacity 0.85J/(g.K), specific surface area 219m 2 Per g, pore volume 0.25cm 3 And/g, average pore size 4.6nm.
TABLE 1
Note that: in tables 1 and 4, I1/I2 is the ratio of the peak intensity at the angle 2θ of 18+ -0.5 ° to the peak intensity at the angle 2θ of 37+ -0.5 ° in the XRD pattern
Example 1
This example illustrates the metal trapping agent and the method of preparing the same.
10.7 parts by weight of the high specific heat capacity matrix material AM-1 prepared in preparation example 1 is added into decationized water, 15 parts by weight (calculated on a dry basis) of halloysite (industrial product of Suzhou porcelain clay company, solid content of 71.6% by weight) is added for pulping, 50 parts by weight of pseudo-boehmite calculated on oxide is added, pH is adjusted to 2 by hydrochloric acid, stirring is uniform, standing and ageing are carried out for 1 hour at 70 ℃, then 20 parts by weight of alumina sol calculated on oxide is added, 4.3 parts by weight of the high specific heat capacity matrix material AM-1 (the weight ratio of the high specific heat capacity matrix materials added before and after ageing is 1:0.4) is added, stirring is carried out uniformly, slurry with the solid content of 24.5% is obtained, the obtained slurry is spray-dried and formed into particles with the diameter of 20-150 micrometers at the temperature of 350 ℃, and roasting is carried out for 2 hours at the temperature of 550 ℃, so that the metal trapping agent C1 provided by the invention is obtained. The composition of C1 is shown in Table 2.
Comparative example 1
This comparative example illustrates a reference catalyst comprising the matrix material DAM-1 prepared in the comparative preparation and its preparation.
A metal trap was prepared as in example 1, except that DAM-1 was used in place of AM-1 in example 1, to give a reference metal trap CB1. The composition of CB1 is shown in Table 3.
Comparative example 2
This comparative example illustrates a reference metal trap containing the matrix material DAM-2 prepared in the comparative preparation and its preparation.
A metal trap was prepared as in example 1, except that DAM-2 was used in place of AM-1 in example 1 to give reference metal trap CB2. The composition of CB2 is shown in Table 3.
Comparative example 3
This comparative example illustrates a reference metal trap without a high specific heat capacity matrix material and its preparation.
A metal trapping agent was prepared as in example 1, except that kaolin was used instead of AM-1 in example 1, with a concentration of 450gMnO 2 MnCl of/L 2 The composition obtained by spray drying the solution was impregnated so that the mass fraction of manganese dioxide on the reference metal collector was 10%, and then calcined to obtain reference metal collector CB3, the composition of CB3 being shown in Table 3.
Example 2
This example illustrates the metal trapping agent and the preparation method thereof.
A metal trap was prepared as in example 1, except that: the metal trapping agent C2 provided by the invention is obtained by adding the pseudo-boehmite and the halloysite into the mixture, adding the high specific heat capacity matrix material AM-2 to replace AM-1 before aging, adding the high specific heat capacity matrix material AM-2 to replace AM-1 after aging, and adding the proportion and the adding amount of the AM-2 before and after aging, wherein the compositions are shown in Table 2. The composition of C2 is shown in Table 2.
Example 3
This example illustrates the metal trapping agent and the preparation method thereof.
A metal trapping agent was prepared as in example 1, except that 30 parts by weight of pseudo-boehmite was used instead of 50 parts by weight of pseudo-boehmite, 25 parts by weight of high specific heat capacity matrix material AM-3 was added before aging instead of 10.7 parts by weight of AM-1, and 10 parts by weight of high specific heat capacity matrix material AM-3 was added after aging instead of 4.3 parts by weight of AM-1, to obtain metal trapping agent C3 provided by the present invention. The composition of C3 is shown in Table 2.
Example 4
This example illustrates the metal trapping agent and the method of preparing the same.
Adding 40 parts by weight of pseudo-boehmite into decationized water, adjusting the pH value to 2 by using nitric acid, uniformly stirring, adding 12.5 parts by weight of high specific heat capacity matrix material AM-4, standing and aging for 5 hours at 50 ℃ to obtain an aged product.
Adding 10 parts by weight of aluminum sol into the aged product, uniformly stirring, adding 37.5 parts by weight of high-specific heat capacity matrix material AM-4, pulping to obtain slurry with the solid content of 27.4% by weight, spray-drying the obtained slurry at 220 ℃ to form particles with the diameter of 20-150 micrometers, and roasting at 520 ℃ for 4 hours to obtain the metal trapping agent C4. The composition of C4 is shown in Table 2.
Example 5
This example illustrates the metal trapping agent and the method of preparing the same.
Pulping 30 parts by weight of pseudo-boehmite in decationizing water, adding 30 parts by weight of halloysite for pulping, adding 25 parts by weight of high specific heat capacity matrix material AM-5 (the high specific heat capacity matrix materials are added before aging), adjusting the pH value to 3 by hydrochloric acid, uniformly stirring, standing and aging for 2 hours at 60 ℃, adding 15 parts by weight of aluminum sol for uniformly stirring to obtain slurry with the solid content of 25.2% by weight, spray-drying the obtained slurry to form particles with the diameter of 20-150 microns, and roasting at 600 ℃ for 1 hour to obtain the metal trapping agent C5. The composition of C5 is shown in Table 2.
Example 6
This example illustrates the metal trapping agent and the preparation method thereof.
A metal trapping agent was prepared as in example 1, except that 45 parts by weight of halloysite was used instead of 15 parts by weight of halloysite, 10 parts by weight of alumina sol was used instead of 20 parts by weight, 50 parts by weight of pseudo-boehmite was changed to 40 parts by weight, 4.3 parts by weight of high specific heat capacity matrix material AM-6 was added before aging instead of 10.7 parts by weight of AM-1, and 0.7 part by weight of high specific heat capacity matrix material AM-6 was added after aging instead of 4.3 parts by weight of AM-1, to obtain the metal trapping agent C6 provided by the present invention. The composition of C6 is shown in Table 2.
TABLE 2
TABLE 3 Table 3
| Number of metal collector | CB1 | CB2 | CB3 |
| MnO 2 Weight percent | 10 | ||
| Type of matrix material | DAM-1 | DAM-2 | - |
| Matrix material content, wt% | 15 | 15 | 0 |
| Matrix material ratio added before and after aging | 1:0.4 | 1:0.4 | |
| Clay species | Halloysite | Halloysite | Halloysite |
| Clay content, wt% | 15 | 15 | 27 |
| Heat resistant inorganic oxide species | Alumina oxide | Alumina oxide | Alumina oxide |
| Content of refractory inorganic oxide, wt% | 70 | 70 | 63 |
Examples 7 to 12
Examples 7-12 are presented to illustrate the heavy metal contamination process of a metal trap and industrial cracking catalyst mixture and the catalytic cracking performance of the metal trap of the present invention for catalytic cracking.
Firstly, analyzing the solid content of an industrial catalytic cracking catalyst C and the metal trapping agent C1-C6 provided by the invention, then physically mixing according to dry basis measurement to obtain a catalyst mixture,
the catalyst mixture was first subjected to cyclic contamination (to deposit Ni, V, fe) on a cyclic aging apparatus, and the Ni, V, fe contents on the catalyst mixture after cyclic contamination are shown in tables 4 and 5,
the cyclic pollution step comprises the following steps: after introducing heavy metals (Ni, V and Fe) into the catalyst mixture by the michigan impregnation method, the catalyst mixture after introducing heavy metals was then loaded into a D-100 apparatus (small fixed fluidized bed) and treated on the D-100 apparatus as follows:
(a) Heating to 600 ℃ at a heating rate of 20 ℃/min under nitrogen atmosphere;
(b) Heating to 780 ℃ at a heating rate of 1.5 ℃/min, keeping the temperature at 780 ℃, and changing the treatment atmosphere in the constant temperature process according to the following steps:
(i) Treating in an atmosphere containing 40% by volume of nitrogen (wherein the nitrogen contains 5% by volume of propylene) and 60% by volume of water vapor for 10 minutes,
(ii) Treating in an atmosphere containing 40% by volume of nitrogen (pure nitrogen, no propylene) and 60% by volume of water vapor for 10 minutes,
(iii) Treating in an atmosphere containing 40% by volume of air and 60% by volume of water vapor for 10 minutes,
(iv) Treating for 10 minutes in an atmosphere containing 40% by volume of nitrogen and 60% by volume of water vapor; then repeating the circulating steps (i) - (iv) once again according to the sequence, and then repeating the step (i) to finish the circulating pollution step;
then the aging step is carried out: aging the catalyst mixture after the cyclic contamination at 788 ℃ in an atmosphere containing 80% by volume of water vapor and 20% by volume of air for 8 hours;
the catalytic performance of the catalyst mixture after cyclic contamination-aging was then examined on an ACE unit, wherein the feedstock was brought into contact with the catalyst mixture at the bottom of the reactor, wherein the properties of the feedstock used are shown in table 4, and the evaluation conditions and results are shown in tables 5 and 6.
Comparative examples 4 to 7
Comparative examples 4-7 are presented to illustrate the heavy metal contamination process of the comparative catalyst mixture and the catalytic cracking performance of the comparative metal trap for catalytic cracking.
Metal contamination and catalytic cracking were carried out according to the methods of examples 7 to 12, except that the catalyst used was a single industrial catalyst C, a mixture of an auxiliary CB1 and a catalyst C provided in comparative example 1, a mixture of an auxiliary CB2 and a catalyst C provided in comparative example 2, a mixture of an auxiliary CB3 and a catalyst C provided in comparative example 3, and Ni, V, fe contents on the catalyst mixture after contamination were shown in tables 5 and 6, and evaluation conditions and results were shown in tables 5 and 6.
TABLE 4 Table 4
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TABLE 5
In the present invention, conversion ratio=gasoline yield+liquefied gas yield+dry gas yield+coke yield, total liquid yield (also called total liquid product yield) =gasoline yield+diesel yield+liquefied gas yield, coke selectivity=coke yield/conversion ratio, dry gas selectivity=dry gas yield/conversion ratio. The catalyst 97c+3c2 used represents a mixture of 97 parts by weight of catalyst C and 3 parts by weight of metal collector C2 on a dry basis, the remaining examples and comparative examples and so on.
As can be seen from the data in Table 5, the addition of the metal trapping agent provided by the invention to the catalytic cracking catalyst, the metal pollutants such as nickel, vanadium, iron and the like, improves the selectivity of coke and dry gas, increases the yield of total liquid products, and reduces the selectivity of dry gas and coke. Therefore, the metal trapping agent can slow down the damage of metal to the catalytic cracking catalyst, and has a good effect of resisting metal pollution.
TABLE 6
As can be seen from the data in Table 6, compared with the comparative metal trapping agents CB1, CB2 and CB3, the metal trapping agent provided by the invention has better metal trapping capability for pollution, can be used for effectively improving the selectivity of coke and dry gas in the catalytic cracking process, and can increase the yield of total liquid products. Surprisingly, it also increases gasoline yield, increases heavy oil conversion, and decreases coke yield.
Preparation example B1
This example illustrates the preparation process of the high specific heat capacity mesoporous matrix material provided by the invention.
Will have a concentration of 350gAl 2 O 3 Al of/L 2 (SO 4 ) 3 Solution and CO 3 2- Ammonium carbonate solution with concentration of 0.10mol/L is mixed at 30 ℃ to form gel, and pH value=7.5 is controlled to obtain slurry BA. To a concentration of 145gMnO 2 MnCl of/L 2 Adding urea into the solution, wherein the molar ratio of urea to manganese ions is 2, and stirring for 30 minutes at room temperature to obtain solution BB. Adding solution BB into slurry BA, aging for 24h at 80deg.C under stirring, cooling to room temperature, and filtering to obtain solid precipitate (dry basis): h 2 O=1: 10, mixing with water, pulping, and mixing according to the weight ratio B 2 O 3 : ammonium borate is added in a weight ratio of high specific heat capacity matrix material dry basis=0.01:1, and the mixture is stirred for 2 hours at 50 ℃, filtered, and the solid precipitate is formed according to the precipitate (dry basis): h 2 O=1: 8 weight ratio was exchanged 3 times at room temperature, each timeExchanging for 0.5 hours, obtaining a washed solid precipitate which is neutral, drying at 120 ℃ for 12 hours to obtain a matrix material precursor, roasting at 550 ℃ for 6 hours, and cooling to room temperature along with a furnace to obtain the high specific heat capacity matrix material provided by the invention, which is marked as BAM-1. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore size of BAM-1 are listed in Table 4.
Elemental analysis (by weight) of BAM-1 with a chemical composition of 29.7MnO 2 ·69.2Al 2 O 3 ·1.1B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Specific heat capacity 1.3J/(g.K), specific surface area 310m 2 Per g, pore volume 0.65cm 3 And/g, average pore size 8.4nm.
Preparation examples B2 to B4
Preparation examples B2-B4 are used for illustrating the preparation process of the mesoporous matrix material with high specific heat capacity.
High specific heat capacity mesoporous matrix materials BAM-2 to BAM-4 were prepared according to the method of preparation example B1, except that the formulation, preparation parameters, elemental compositions, specific heat capacities, specific surface areas, pore volumes and average pore diameters thereof are shown in Table 4.
Preparation example B5
Preparation example B5 is used for explaining the preparation process of the mesoporous matrix material with high specific heat capacity.
Will have a concentration of 350gAl 2 O 3 Al (NO) 3 ) 3 Solution and CO 3 2- Ammonium carbonate and OH at a concentration of 0.30mol/L - Aqueous ammonia solution with concentration of 0.1mol/L is mixed into gum, and pH=10.5 is controlled to obtain slurry BA. Mn is added to 3 O 4 Mixing with hydrochloric acid and water to obtain 201.7gMnO 2 And (3) controlling the pH value of the manganese chloride solution to be=6, adding urea into the solution, wherein the molar ratio of urea to manganese ions is 3, and stirring the solution at room temperature for 40 minutes to obtain solution BB. Adding solution BB into slurry BA, stirring and aging for 24 hours at 60 ℃, cooling the system to room temperature, and filtering to obtain solid precipitate according to the precipitate (dry basis): h 2 O=1: 10, mixing with water, pulping, and mixing according to the weight ratio B 2 O 3 : the resulting high specific heat capacity matrix material dry basis = 0.01:1, adding ammonium borate, and stirring at 50deg.CFiltering for 2 hours, washing with water (namely washing with water), drying at 120 ℃ for 12 hours to obtain a matrix material precursor, roasting at 650 ℃ for 4 hours, and cooling to room temperature along with a furnace to obtain the matrix material provided by the invention, which is marked as BAM-5. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore size of BAM-5 are listed in Table 4.
Elemental analysis (by weight) of BAM-5 with a chemical composition of 34.8MnO 2 ·60.4Al 2 O 3 ·4.8B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Specific heat capacity 1.43J/(g.K), specific surface area 338m 2 Per g, pore volume 0.94cm 3 And/g, average pore diameter 11.1nm.
Preparation example B6
Preparation example B6 is used for explaining the preparation process of the mesoporous matrix material with high specific heat capacity.
A matrix material BAM-6 was prepared in the same manner as in preparation example B5, except that the formulation, preparation parameters, elemental composition, specific surface area, pore volume and average pore diameter were as shown in Table 4.
TABLE 7
Example 13
A metal trapping agent was prepared as in example 1, except that BAM-1 was used instead of AM-1, to obtain metal trapping agent BC1 provided by the present invention. The composition of BC1 is shown in Table 8.
Example 14
A metal trapping agent was prepared as in example 1, except that BAM-2 was used instead of AM-1 to obtain metal trapping agent BC2 provided by the present invention. The composition of BC2 is shown in Table 8.
Example 15
A metal trapping agent was prepared as in example 1, except that BAM-3 was used instead of AM-1 to obtain metal trapping agent BC3 provided by the present invention. The composition of BC3 is shown in Table 8.
Example 16
A metal trapping agent was prepared as in example 1, except that BAM-4 was used instead of AM-1 to obtain metal trapping agent BC4 provided by the present invention. The composition of BC4 is shown in Table 8.
Example 17
A metal trapping agent was prepared as in example 1, except that BAM-5 was used instead of AM-1 to obtain metal trapping agent BC5 provided by the present invention. The composition of BC5 is shown in Table 8.
Example 18
A metal trapping agent was prepared as in example 1, except that BAM-6 was used instead of AM-1 to obtain metal trapping agent BC6 provided by the present invention. The composition of BC6 is shown in Table 8.
TABLE 8
Examples 22 to 27
Examples 22-27 are presented to demonstrate the performance testing of the catalytic cracking metal collector provided by the present invention.
The metal contamination and catalytic cracking reaction were evaluated in the same manner as in examples 7 to 12, and the Ni, V and Fe contents of the contaminated metal collector mixture are shown in Table 9, and the evaluation conditions and results are shown in Table 9.
TABLE 9
In table 9, the catalyst row, 94c+6bc1, represents a mixture of 94 parts by weight of the catalytic cracking catalyst C and 6 parts by weight of the metal collector BC1 on a dry basis, and so on.
From the heavy oil evaluation results in tables 5, 6 and 9, it can be seen that the catalyst mixture sample containing the metal trapping agent provided by the invention shows more excellent heavy oil cracking performance, higher conversion rate, significantly reduced heavy oil yield, improved gasoline yield, significantly higher total liquid yield and optimized product distribution while maintaining good coke selectivity after metal contamination. Therefore, the metal trapping agent provided by the invention has better heavy oil conversion capability, can improve the gasoline yield, improves the total liquid yield, and reduces the coke selectivity and the dry gas selectivity.
Claims (21)
1. A multifunctional metal trap, the metal trap comprising, based on the total weight of the metal trap:
(a) 1-60 wt% of a high specific heat capacity matrix material; wherein the specific heat capacity of the high specific heat capacity matrix material at 1000k is 1.3-2.0J/(g.K), and the specific surface area of the high specific heat capacity matrix material is 150-500m 2 •g -1 The pore volume of the high specific heat capacity matrix material is 0.3-1.5cm 3 •g -1 The high specific heat capacity matrix material has an average pore diameter of 3-20 nm; the XRD pattern of the high specific heat capacity matrix material has an intensity ratio of 1 between peaks at an angle of 18+/-0.5 DEG for 2 theta and an angle of 37+/-0.5 DEG for 2 theta: (3-10);
the high specific heat capacity matrix material consists of 15-70 wt% of manganese oxide and 30-85 wt% of aluminum oxide, or,
the high specific heat capacity matrix material consists of 15-80 wt% of aluminum oxide, 15-70 wt% of manganese oxide and 5-30 wt% of boron nitride; or alternatively
The high specific heat capacity matrix material consists of 15-80 wt% of alumina and MnO 2 15-80 wt% manganese oxide and B 2 O 3 0.8 to 8% by weight of boron oxide;
(b) 40-99 wt% of a refractory inorganic oxide; and
(c) 0-50% by weight of clay, and the clay content is other than 0.
2. The multifunctional metal trap according to claim 1, wherein the metal trap contains (a) 5 to 50% by weight of a high specific heat capacity matrix material, (b) 40 to 70% by weight of a heat resistant inorganic oxide, and (c) 0 to 45% by weight of clay, based on the total weight of the metal trap, and the clay content is not 0.
3. The multifunctional metal collector according to claim 1, wherein the high specific heat capacity matrix material consists essentially of 30 to 61 wt% of manganese oxide and 39 to 70 wt% of aluminum oxide, or,
the high specific heat capacity matrix material consists of 19-74 wt% of aluminum oxide, 19-66 wt% of manganese oxide and 8-26 wt% of boron nitride; or alternatively
The high specific heat capacity matrix material consists of 20-62 wt% of aluminum oxide and MnO 2 34-72 wt% manganese oxide and B 2 O 3 2-8% by weight of boron oxide.
4. A multifunctional metal trap according to any one of claims 1-3, wherein the high specific heat capacity matrix material is prepared by a preparation method comprising the steps of:
(1) Mixing an aluminum source with alkali to form a colloid containing aluminum, wherein the pH value of the colloid containing aluminum is 7-11;
(2) Mixing manganese salt solution with pH value of 3-7 with urea to obtain manganese source solution;
(3) Forming a mixture of an aluminum-containing colloid, a manganese source solution, and optionally a boron compound; and optionally
(4) Washing and/or drying and/or calcining.
5. The multifunctional metal collector of claim 4, wherein the mixing the aluminum source with the base into a gel comprises: mixing an aluminum source solution and an alkali solution to form a colloid with a temperature of between room temperature and 85 ℃ and a pH value of 7-11, wherein the concentration of aluminum oxide in the aluminum source solution is 150-350gAl 2 O 3 The concentration of alkali in the alkali solution is 0.1-1mol/L, and the aluminum source is one or more selected from aluminum nitrate, aluminum sulfate, aluminum phosphate and aluminum chloride; the alkali is water-soluble carbonate, water-soluble bicarbonate or water-soluble hydroxideOne or more of the following.
6. The multifunctional metal collector according to claim 5, wherein the solution of the base is selected from the group consisting of a solution containing CO 3 2- 、HCO 3 - Or OH (OH) - An aqueous alkaline solution of one or more of the bases, CO in the alkaline solution 3 2- The concentration of (C) is 0-0.6mol/L, OH - The concentration of (C) is 0-0.5mol/L, HCO 3 - The concentration of (C) is 0-1mol/L.
7. The multifunctional metal collector according to claim 4, wherein in the step (2), the molar ratio of urea to manganese ions is 1 to 5, and the concentration of manganese salt in the manganese salt solution is represented by MnO 2 50-500g.L -1 。
8. The multifunctional metal collector of claim 7, wherein in step (2), the molar ratio of urea to manganese ions is 2-4.
9. The multifunctional metal collector according to claim 4, wherein urea is added to the manganese salt solution in step (2), and then stirred at room temperature for 30-60 minutes to obtain a manganese source solution.
10. The multifunctional metal collector according to claim 4, wherein the boron compound is boron nitride and/or boron oxide precursor, and the boron nitride is at least one selected from hexagonal boron nitride, cubic boron nitride, diamond Fang Danhua boron and wurtzite boron nitride; the boron oxide precursor is one or more of ammonium borate, ammonium hydrogen borate or boric acid.
11. The multifunctional metal collector according to claim 4, wherein the step (3) further comprises an aging process after the aluminum-containing colloid and the manganese source solution are mixed, wherein the aging temperature is from room temperature to 120 ℃, the aging time is from 4 to 72 hours, and the aging is performed under stirring or standing aging.
12. The multifunctional metal collector according to claim 11, wherein the aging is performed under stirring at 60-100 ℃ for 12-36 hours.
13. The multifunctional metal collector according to claim 4, wherein the boron compound is boron nitride; the method for forming the mixture of the aluminum-containing colloid, the manganese source solution and the boron compound in the step (3) is as follows: mixing an aluminum-containing colloid, a manganese source solution and a boron compound, and aging; alternatively, the boron compound is boron oxide and/or a precursor of boron oxide, and the method for forming a mixture of the aluminum-containing colloid, the manganese source solution and the boron compound in the step (3) is as follows: mixing an aluminum-containing colloid, a manganese source solution, aging, optionally washing, and then mixing with a boron compound.
14. The multifunctional metal collector according to claim 4, wherein the firing temperature in step (4) is 500 ℃ to 900 ℃ and the firing time is 4 to 8 hours.
15. The multifunctional metal collector according to claim 1 or 2, wherein the heat-resistant inorganic oxide is one or more selected from the group consisting of alumina, silica and amorphous silica-alumina; the clay is one or more selected from kaolin, halloysite, montmorillonite, diatomite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
16. A method of preparing the multifunctional metal collector of any one of claims 1-15, the method comprising: forming a first slurry comprising a high specific heat capacity matrix material, a refractory inorganic oxide and/or a refractory inorganic oxide precursor, water, and optionally clay, drying, and firing.
17. The method for preparing a multifunctional metal trap according to claim 16, wherein the method for preparing comprises:
mixing the first high specific heat capacity matrix material, the heat resistant inorganic oxide and/or heat resistant inorganic oxide precursor, water, an acid and optionally clay to form a second slurry with a pH value of 1-5, aging, and optionally adding a second high specific heat capacity matrix material; the acid is one or more of inorganic acid and organic acid which can be dissolved in water.
18. The method for preparing a multifunctional metal trapping agent according to claim 17, wherein the aging is performed at a temperature of 20-60 ℃ for 0.1-5 hours; the acid is one or more of inorganic acid and organic acid which can be dissolved in water, and the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid and acetic acid.
19. The method of claim 17, wherein the weight ratio of the first high specific heat capacity matrix material to the second high specific heat capacity matrix material is 1: (0.1-6).
20. The method of claim 19, wherein the weight ratio of the first high specific heat capacity matrix material to the second high specific heat capacity matrix material is 1: (0.1-3).
21. A catalytic cracking process comprising the step of contacting a hydrocarbon oil with a catalyst, wherein the catalyst comprises a catalytic cracking catalyst and a metal trap, the metal trap being a multifunctional metal trap as defined in any one of claims 1 to 15.
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| JP2005179101A (en) * | 2003-12-17 | 2005-07-07 | Kyocera Corp | Forsterite raw material composition and method of manufacturing forsterite sintered compact using the same |
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