CN101583696A - 用于催化裂化过程的捕钒剂及其制备 - Google Patents
用于催化裂化过程的捕钒剂及其制备 Download PDFInfo
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- CN101583696A CN101583696A CNA2007800494349A CN200780049434A CN101583696A CN 101583696 A CN101583696 A CN 101583696A CN A2007800494349 A CNA2007800494349 A CN A2007800494349A CN 200780049434 A CN200780049434 A CN 200780049434A CN 101583696 A CN101583696 A CN 101583696A
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- Prior art keywords
- chemical composition
- vanadium
- magnesium
- pyrophosphate
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 50
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 10
- 230000008569 process Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 12
- 239000000203 mixture Substances 0.000 claims abstract description 45
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 25
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 5
- 239000011029 spinel Substances 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 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 13
- 235000019253 formic acid Nutrition 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 241001460678 Napo <wasp> Species 0.000 claims description 11
- RCUAPGYXYWSYKO-UHFFFAOYSA-J barium(2+);phosphonato phosphate Chemical compound [Ba+2].[Ba+2].[O-]P([O-])(=O)OP([O-])([O-])=O RCUAPGYXYWSYKO-UHFFFAOYSA-J 0.000 claims description 9
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 9
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 9
- 235000019821 dicalcium diphosphate Nutrition 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
- 239000007787 solid Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 4
- 150000002681 magnesium compounds Chemical group 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- -1 magnesium aluminate Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 229910013832 M2P2O7 Inorganic materials 0.000 abstract 3
- 235000011180 diphosphates Nutrition 0.000 abstract 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract 1
- 239000000347 magnesium hydroxide Substances 0.000 abstract 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 12
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004480 active ingredient Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001679 gibbsite Inorganic materials 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 5
- HJXDCFUIDHJETK-UHFFFAOYSA-N 3-(2-hydroxypropyl)-5-methyl-1,3-oxazolidin-2-one Chemical compound CC(O)CN1CC(C)OC1=O HJXDCFUIDHJETK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 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
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000516 activation analysis Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及化学组合物,其能够被用于具有钒污染物的烃催化裂化过程,包括由不同的焦磷酸盐M2P207(M=Ba或Ca)负载于氧化镁和氧化铝混合物上形成的活性相,优选尖晶石相铝酸镁。所述组合物捕捉源自原料的金属,特别是钒,并因此保护催化剂。所述组合物优选以分散颗粒的形式使用,以根据所述原料的金属含量控制其加入到设备中。本发明也涉及制备所述组合物的方法,包括合成焦磷酸盐、形成水铝矿矾土、氧化镁或氢氧化镁与氧化物M2P207的悬浮液、喷雾干燥并煅烧微球而不产生氧化物M2P207的晶体结构的任何损失。
Description
技术领域
本发明涉及能够处理具有高金属含量特别是钒的原料的化学组合物,以在SO2的存在下捕捉所述金属,并以这种方式下保持工业加工单元中裂化催化剂的活性和选择性。这些组合物的制备方法也是本发明的一部分,其允许保持它们的活性相(焦磷酸钡或焦磷酸钙)的晶体结构,并同时提供最低物理性质使其用作工业单元中的添加剂。
现有技术
流体催化裂化单元的主要操作问题之一是由随原料进入的金属(例如钒和钠)的作用而引起的催化剂活性的不可逆的损失。发生在再生器的高度苛刻的水热条件下的催化剂的破坏,不仅降低了有价值产品的收率,而且明显增加了由向所述单元中增添新鲜催化剂引起的生产成本。
文献中已经提出了解决该问题的两种不同方法,一些改进了催化剂的个别组分例如沸石和基质的耐钒性能,和其它的将捕钒剂加入到催化剂藏量中。
文献中不同的取得专利的组分之中,稀土氧化物以工业水平重点应用,尤其是La2O3(美国专利号5603823、5077263、5001096、4900428、4515683、4921824、5304299和5364516)。文献报道,基于La2O3的添加剂RV4,一种捕钒剂,能够仅20%地抵消平衡催化剂中钒的破坏作用,这在不同的工业应用中被观察到。
其它工业上使用的活性组分,但从它们中得不到它们的工业应用的结果,对应于加入到催化剂制剂中的(US专利号4988654)或以独立颗粒作为添加剂(US专利号5002653和5071807)的纯的碱土金属氧化物例如MgO和CaO或其与含有钙和镁的物质例如白云石、海泡石的混合物。
向以上信息中可以加入以下信息:相当一部分周期表元素已经以元素形式或相关的氧化物和磷酸盐形式被专利化为捕钒剂的活性组分。
当前,用于捕钒剂的活性组分不能单独加入到工业单元中。它们能在催化剂制备过程中加入到催化剂中形成整体颗粒,或被沉积在载体上形成独立的颗粒。独立颗粒化学组合物的使用呈现了能够根据单元的需要加入到***中的优势。
独立颗粒捕钒剂是催化裂化化学组合物(流体催化裂化,FCC),并且同样必须具有与FCC催化剂相同的特点,即:尺寸、尺寸分布、形状和用以承受工业单元中存在的极端工业条件的机械强度,并可以是催化剂的最重要的性质,其是充分暴露的活性面积,也就是活性化合物最大的分散性和可接近性。
具有这些特点的化学组合物基本上由三个组分组成:载体、活性相和粘结剂。所述载体用于提供捕捉剂机械强度和结构性质,例如比表面积、孔容和平均孔径。所述粘结剂的功能,如其名字指出的,是维持所述载体和所述活性组分之间的坚固粘结,因此保证最终产物的形貌和对于磨损的机械强度性质。
对于所述化学组合物的载体和粘结剂的适当选择决定其在工业单元中的可靠性,因为活性组分-粘结剂或活性组分-载体的相互作用两者都能导致形成对于捕捉钒来说新的无活性化合物。
从上述可知,文献中捕钒剂的使用显然不是新的,然而且尽管存在一长列的能够抵消钒影响的物质,在大多数情况下,它们的结果仅在实验室规模下有前景。与工业应用的差异已经被归因于工业操作中硫化合物SOx的存在,其妨碍捕捉剂捕捉钒的能力。
美国专利6159887报道了实验室中一些更有前景的组分,其公开了能够抵消稳定的Viv和Vv化合物形式的钒的不同的磷无机化合物,例如M(PO3)2、M2P2O7、M3(PO4)2、M10(OH)2(PO4)6、M(H2PO4)2、MHPO4、3M3(PO4)2·MCO3、M(H2PO2)2、MHPO3、M(PO2)2、M2P2O7、M3(PO4)2、M10(OH)2(PO4)6、M(H2PO4)2、MHPO43M3(PO4)2·MCO3、M(H2PO2)2、MHPO3、M(PO2)2、M2P2O6和A(PO3)3,其中M代表二价金属,例如Be、Mg、Ca、Sr、Ba、Zn、Cd和Pb,和A代表三价金属,例如Al、Ga、In、As、Sb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd。根据该应用,对于在裂化催化剂中直接用于钒固定显示最好结果的磷化合物是Ba(PO3)2、Ba2P2O7、Ba3(PO4)2、Ba10(OH)2(PO4)6和它们的混合物。
据报道,焦磷酸钡(PBA)和焦磷酸钙(PCA)通过REDOX机理能抵消钒的破坏作用,该机理不同于文献中报道的其中碱性活性组分与酸性钒氧化物反应的机理。该性质能避免由工业再生器中存在的硫氧化物SOx引起的活性组分的不想要的抵消反应。
美国专利6159887也报道了通过将PBA和PCA沉淀在不同载体上而制备PBA和PCA捕捉剂,所述载体例如:矾土、氧化硅、氧化镁、硅酸铝等。引用的专利中用所述活性剂和载体制备的不同制剂使我们注意到,负载于氧化硅、矾土或氧化硅-矾土上的PBA完全分解为不同类型的磷酸盐(例如Ba3(PO4)2、AlPO4、BaHPO4和Ba8Al2011)和氧化物(其在SOx的存在下没有显示任何捕捉钒的能力),因此使得该捕捉剂变得没有用处。除已被提到的以外,在MgO作为载体的情况下,它显示了低的表面积和在水的存在下高的烧结倾向,因此使用该载体的捕捉剂设计是不方便的。
另一方面,使用不同的粘结剂(例如羟铝基氯化物(chlorhydrol)或硅酸钠)基于PBA的捕捉剂制剂,使得通过DRX衍射光谱分析显示,PBA在这些制剂中分解,导致不同的具有磷和钡的氧化铝和氧化硅。
这些先例导致以下观点的确立:在现有技术下不能解决在用于催化裂化过程的基于焦磷酸钡和焦磷酸钙的捕钒剂的制备中所涉及到的所有不便之处,因为它们对通常使用的载体(例如矾土和氧化硅)的羟基展现了高的反应性,这导致这些磷酸盐的破坏并阻碍了有效捕捉剂的生产。
因为PBA或PCA是一些在SOx的存在下最有前景的捕钒剂,至少在实验室中,希望具有克服了前述不便之处的捕捉剂或允许生产捕捉剂的方法。
本发明提供一个配方和制备捕钒剂的方法,其不仅克服了上述暴露出的不便之处,而且证明在催化裂化单元中处理重质原料时能够保护所述催化剂,优于任何其它本领域现有的催化剂。
发明详述
本申请的要求保护的发明在烃催化裂化过程中是有用的,其中钒以原料毒物的形式存在并破坏该过程中使用的催化剂组分,降低它们的活性和有价值的产物例如汽油的收率。为了避免催化剂中毒和破坏,有必要使用与所述催化剂竞争钒的添加剂。申请人已经确立,应用负载在铝基基质或镁基基质上的PBA或PCA,使它们在催化裂化过程的条件下与钒反应形成稳定的化合物,其中所述钒被稳定在其IV和V氧化态上。
因此,本发明的第一方面提供了用于含钒污染物的烃催化裂化过程的化学组合物,其特征在于它包含焦磷酸盐M2P2O7(其中M=Ba或Ca)和与不同的镁化合物结合的氧化铝载体,所述镁化合物例如MgO、Mg(OH)2或任何可溶的盐例如Mg(NO3)2。
特别地,本发明涉及包含焦磷酸钡或焦磷酸钙和尖晶石相铝酸镁载体的组合物。
本发明的组合物特征在于它包含10-60wt%的焦磷酸钡或焦磷酸钙、60-90wt%的氧化铝和10-40wt%的氧化镁。优选它包含30wt%的焦磷酸钡或焦磷酸钙、55wt%的氧化铝和15wt%的氧化镁。
在第二方面,本申请也涉及本发明的组合物的生产方法,其包括:
-通过煅烧由两种溶液共沉淀产生的前体盐BaHPO4或CaHPO4制备所述焦磷酸盐,第一种是磷源例如(NH4)2HPO4或H3PO4,和第二种是硝酸盐或氯化物形式的Ba或Ca源,选自Ba(NO3)2和BaCl2。通过在高速搅拌下向上述溶液中加入NH4OH溶液直到pH超过7.5进行共沉淀以获得具有小于1μm的颗粒尺寸的BaHPO4或CaHPO4。然后在750℃和820℃之间的温度下煅烧这些固体,以分别获得颗粒尺寸约为1μm的PBA和PCA。
-在无机酸(例如HNO3、HCl)或有机酸(例如乙酸、甲酸等)的存在下,通过氧化铝(优选水铝矿型氢氧化铝)的部分溶解单独制备所述载体。老化时间后,将MgO或氢氧化镁悬浮液加入到所述矾土悬浮液中,通过加入NH4OH溶液调节pH超过4.0,优选超过4.5。
-然后向前面步骤的载体中加入如上所述获得的PBA或PCA悬浮液,和最后通过喷洒法干燥所得到的悬浮液,以获得捕钒剂微球,其具有用在工业过程中所需要的机械强度。
使用该步骤,所述活性相的晶体结构得以保持并具有其最大的捕钒能力。这种形式的钒固定比传统的酸-碱机理有优势,因为它避免或最小化了硫酸对正常使用的捕钒剂的竞争。
给出以下实施例以阐述本发明的目标和优势。但是,它们不打算限制本发明的范围。
实施例1:
为了制备80g的样品,使用以下试剂:
-水铝矿型氢氧化铝 100g
-98%甲酸 55.1g
-六偏磷酸钠(NaPO4)6 0.3g
-去离子水 178.2g
将分散剂(NaPO4)6加入到水中,然后加入甲酸,接下来加入氢氧化铝,以形成30wt%的悬浮液,然后将其剧烈搅拌。最后,通过加入浓氢氧化铵调节pH值超过4.5。
将最终的悬浮液放入干燥器装载容器。将干燥并过筛的最终样品在马弗炉中在750℃和820℃之间的温度下煅烧2小时。
实施例2:
为了制备133.3g的样品,使用以下试剂:
-水铝矿型氢氧化铝 112.15g
-悬浮液中的MgO 20g
-98%甲酸 29.5g
-六偏磷酸钠(NaPO4)6 0.4g
-去离子水 200g
将分散剂(NaPO4)6加入到水中,然后加入甲酸,接下来加入氢氧化铝,以形成30wt%的悬浮液,然后将其剧烈搅拌。然后加入MgO悬浮液,并剧烈搅拌所述混合物。最后,通过加入浓氢氧化铵调节pH值超过4.5。
最后,将所述悬浮液放入干燥器装载容器。将干燥和过筛的最终样品在马弗炉中在750℃和820℃之间的温度下煅烧2小时。
实施例3:
为了制备153.3g样品,使用以下试剂:
-水铝矿型氢氧化铝 112.15g
-悬浮液中的MgO 40g
-98%甲酸 29.5g
-六偏磷酸钠(NaPO4)6 0.4g
-去离子水 200g
将分散剂(NaPO4)6加入到水中,然后加入甲酸,接下来加入氢氧化铝,以形成30wt%的悬浮液,然后将其剧烈搅拌。然后加入MgO悬浮液,并剧烈搅拌所述混合物。最后,通过加入浓氢氧化铵调节pH值超过4.5。
将最终的悬浮液放入干燥器装载容器中。将干燥和过筛的最终样品在马弗炉中在750℃和820℃之间的温度下煅烧2小时。
实施例4:
为了制备50g样品,使用以下试剂:
-水铝矿型氢氧化铝 53.5g
-颗粒尺寸小于1μm的PBA 15g
-98%甲酸 29.5g
-六偏磷酸钠(NaPO4)6 0.1606g
-去离子水 95.4g
将分散剂(NaPO4)6加入到水中,然后加入甲酸,接下来加入氢氧化铝,以形成30wt%的悬浮液,然后将其剧烈搅拌。然后通过加入浓氢氧化铵溶液将该悬浮液pH增加到4.0。将PBA与水以1/1的比例并行放入悬浮液中,并剧烈搅拌。
将所述PBA悬浮液加入到所述氢氧化铝中,并持续搅拌1分钟。
将最终的悬浮液放入干燥器装载容器中。将干燥和过筛的最终样品在马弗炉中在750℃和820℃之间的温度下煅烧2小时。
实施例5:
为了制备133.3g的制品,使用以下试剂:
-水铝矿型氢氧化铝 112.5g
-颗粒尺寸小于1μm的PBA 40g
-悬浮液中的MgO 20g
-98%甲酸 29.5g
-六偏磷酸钠(NaPO4)6 0.4g
-去离子水 200g
将分散剂(NaPO4)6加入到水中,然后加入甲酸,接下来加入氢氧化铝,以形成30wt%的悬浮液,然后将其剧烈搅拌。然后加入MgO悬浮液,继续剧烈搅拌。然后,通过加入浓氢氧化铵调节所述悬浮液的pH超过4.0。
最后,随着继续搅拌,加入粉末形式的PBA。
最后,将所述悬浮液放入干燥器装载容器中。将干燥和过筛的最终样品在马弗炉中在750℃和820℃之间的温度下煅烧2小时。
在水热条件下评价捕捉剂
通过由溶解在环己烷中的钒源(3.4%钒富集的瓦斯油)进行初始浸渍,使新鲜商业催化剂混合物CATF和10wt%的捕钒剂样品浸渍了0.6wt%的钒。该固体在马弗炉中煅烧,最初加热到120℃的温度,在2个多小时过程中维持该温度恒定。然后以10℃/min的速率快速升温到600℃,并将所述固体在该温度下放置2个多小时。
煅烧后,将具有或没有钒的CATF样品和CATF/样品/0g)的混合物在干燥空气流下放入连续流且固定床的反应器中。所述固体以3-4℃/min的速率温和加热到815℃。一旦达到该温度,通过维持液态水为45℃恒温的饱和器通入空气。在这样的条件下,所述空气流以18%的水(摩尔分数)进行饱和,该物流在20.5小时期间内通过所述催化剂床层。该期间结束时,在1个多小时期间内将该失活物流转变成相同温度下的干燥氮气,然后快速冷却该***至室温,维持干燥氮气流。
表1和2显示了根据前述实施例1-5制备的捕捉剂的表征和失活后混合物的MAT微活性分析的结果。
表1.样品表征
**从DRX中的PBA衍射强度针对2θ=23°的值测量的,并与纯PBA的强度进行比较。
表2.具有或没有钒的CATF和具有在不同的实施例中制备的样品的CATF混合物的MAT结果,不存在SO2。
收率wt% | 催化剂0%V | 催化剂0.6%V | 1 | 2 | 3 | 4 | 5 |
H2 | 0.1 | 0.6 | 0.7 | 0.3 | 0.5 | 0.4 | 0.2 |
干燥气体 | 4.7 | 3.4 | 2.0 | 1.6 | 2.9 | 1.5 | 1.4 |
LPG | 16.4 | 11.3 | 10.0 | 9.8 | 9.2 | 8.3 | 9.5 |
C5-220℃ | 48.7 | 41.5 | 44.8 | 51.6 | 44.9 | 48.8 | 49.9 |
ALC | 15.3 | 20.7 | 22.3 | 20.2 | 22.0 | 22.4 | 21.1 |
Clarif.油 | 5.9 | 16.3 | 13.1 | 8.9 | 14.4 | 11.8 | 10.6 |
焦炭 | 8.9 | 6.7 | 7.8 | 7.9 | 6.6 | 7.3 | 7.5 |
转化率X% | 78.8 | 63 | 64.6 | 71 | 63.6 | 65.8 | 68.3 |
LPG+汽油 | 65.2 | 52.8 | 54.8 | 61.4 | 54.2 | 57 | 59.4 |
%保护作用汽油+LPG | 100 | 0 | 16.0 | 69.1 | 10.5 | 33.8 | 53.2 |
%保护作用沸石面积 | 100 | 0 | 26.6 | 77.2 | 32 | 48.1 | 64 |
从这两个表中显示的结果可以观察到,载体本身,它是矾土或矾土-MgO的混合物,在水热条件下具有作为捕钒剂的性质。
当使用21.5%MgO和78.5%矾土的混合物时,能够观察到对有价值产物(汽油+GLP)的保护作用为69.1的尖晶石相的铝酸镁的形成,但当该混合物中存在过量MgO时,如实施例3中所发生的,对有价值产物的保护作用降低到10.5%。后者证明在尖晶石相的铝酸镁中的游离相MgO是有害的。
在实施例4中,样品的另一个令人感兴趣的方面是,除了在制备时PBA已经被完全破坏的事实以外,能够看到保护作用超过在纯矾土中的保护作用。
还值得强调的是,实施例2中的铝和MgO的组合和由实施例5生产的本发明的添加剂制剂呈现了最好的保护性质。
在SO2的存在下通过CPS循环评价捕捉剂
将商业催化剂、捕捉剂和8000ppm钒的混合物(100g)用于流化床中进行还原-氧化循环失活过程(40次循环)。
在于马弗炉中焙烧后和达到失活温度后,使氮气流在10分钟内通过所述床层,以清除吸附在催化剂上的氧气。在第二步中,使包含50%丙烯和50%蒸汽的物流通过催化剂的流化床,持续又一个10分钟。然后再次使用氮气流在10分钟内对所述催化剂进行清除,最终使用包含50%空气(该空气中含有4体积%的SO2)和50%蒸汽的物流进行处理。该步骤重复40次。在整个步骤中温度保持恒定在788℃。
表3显示了具有0.8wt%钒的催化剂、没有钒的催化剂和具有10wt%的所制备的不同样品的催化剂混合物(这些混合物已经浸渍了0.8wt%的钒)的MAT微活性结果。
表3.在SO2的存在下REDOX循环中失活的固体的MAT微活性结果
收率wt% | 催化剂 | 催化剂0.8%p V | 1 | 2 | 5 |
H2 | 0.17 | 0.20 | 0.4 | 0.45 | 0.19 |
干燥气体 | 1.7 | 0.77 | 1.2 | 1.32 | 0.87 |
LPG | 11.6 | 4.5 | 4.3 | 5.1 | 7.0 |
C5-220℃ | 49.4 | 38.2 | 36.5 | 34.4 | 44.8 |
ALC | 21.2 | 25.5 | 26.4 | 26.4 | 25.2 |
Clarif.油 | 11.5 | 27.1 | 26.7 | 26.6 | 17.2 |
焦炭 | 4.6 | 3.9 | 4.4 | 6.3 | 4.9 |
转化率X% | 67.3 | 47.4 | 46.8 | 47.1 | 57.6 |
LPG+汽油 | 61 | 42.7 | 40.8 | 39.5 | 51.7 |
%保护作用汽油+LPG | 100 | 0.0 | 0.0 | 0.0 | 49.3 |
%保护面积沸石 | 100 | 0.0 | 0.0 | 0.0 | 20.1 |
从显示的结果中能够突出显示由矾土或矾土和氧化镁的混合物构成的载体,当在SO2(在空气中为2摩尔%)的存在下是如何没有显示任何类型的捕捉钒的能力的,这不同于使用水蒸汽和空气的失活。这解释了现有技术中报道的作为捕钒剂的固体不能在SO2(与工业单元的场景相似)的存在下同样发挥作用的原因。
与此相反,由PBA负载于氧化铝和氧化镁的混合物上构成的固体,与商业催化剂和钒混合,并在SO2的存在下,近似维持了与在水热失活中观察到的对有价值产物的收率的相同的保护能力。
Claims (14)
1.用于含钒污染物的烃催化裂化过程的化学组合物,其特征在于它包含焦磷酸盐M2P2O7,其中M=Ba或Ca,和与不同的镁化合物结合的氧化铝载体,所述镁化合物例如MgO、Mg(OH)2或任何可溶的盐例如Mg(NO3)2。
2.根据权利要求1的化学组合物,其特征在于所述载体优选尖晶石相的镁酸铝。
3.根据前述权利要求中任一项的化学组合物,其特征在于所述焦磷酸钡或焦磷酸钙的含量在5wt%至60wt%之间。
4.根据权利要求3的化学组合物,其特征在于所述焦磷酸钡或焦磷酸钙的含量优选为30wt%。
5.根据前述权利要求中任一项的化学组合物,其特征在于所述氧化铝的含量在40wt%至90wt%之间。
6.根据权利要求5的化学组合物,其特征在于所述氧化铝的含量为55wt%。
7.根据前述权利要求中任一项的化学组合物,其特征在于所述氧化镁的含量在5wt%至30wt%之间。
8.根据权利要求7的化学组合物,其特征在于所述氧化镁的含量为15wt%。
9.根据前述权利要求中任一项的化学组合物,其特征在于它包含5-60wt%的焦磷酸钡或焦磷酸钙、40-90wt%氧化铝和5-30wt%氧化镁。
10.生产前述权利要求的化学组合物的方法,其特征在于它包括以下步骤:
a)通过共沉淀和煅烧BaHPO4或CaHPO4制备所述焦磷酸盐,该步骤是:
i)将具有磷源例如(NH4)2HPO4或H3PO4的溶液与具有硝酸盐或氯化物类型的Ba或Ca源例如Ba(NO3)2和BaCl2的溶液混合,
ii)加入NH4OH溶液以达到pH超过7.5并在高搅拌速度下使上述溶液共沉淀,结果是具有小于1μm的颗粒尺寸的BaHPO4或CaHPO4,
iii)在750℃至820℃之间煅烧上述步骤的固体,以获得具有接近1μm的颗粒尺寸的PBA和PCA,
b)根据以下步骤制备所述载体:
i)在无机酸例如HNO3、HCl或有机酸例如乙酸、甲酸等的存在下,部分溶解氧化铝,优选矾土,
ii)加入MgO或氢氧化镁悬浮液,
iii)通过加入NH4OH溶液调节pH超过4.0,优选超过4.5,
c)向所述载体中加入PBA或PCA悬浮液,并通过喷洒法干燥。
11.根据权利要求10的方法,其特征在于在阶段b)的第一步骤中所用的酸优选是甲酸。
12.根据权利要求10或11的方法,其特征在于所述阶段b)的第一步骤包括加入分散剂。
13.根据权利要求10的方法,其特征在于所述阶段b)的第一步骤包括加入浓度在0.1%和2%之间的(NaPO4)6分散剂。
14.根据权利要求1-9中任一项的化学组合物,其特征在于它是使用根据权利要求10-13中任一项的方法获得的。
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CN103785427A (zh) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | 一种金属捕集剂及其制备方法和应用以及一种催化裂化方法 |
CN104226236A (zh) * | 2013-06-14 | 2014-12-24 | 中国石油化工股份有限公司 | 金属捕集剂以及催化裂化方法 |
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Cited By (7)
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CN103785346A (zh) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | 一种金属捕集剂及其制备方法和应用以及一种催化裂化方法 |
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