CN1317359C - Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite - Google Patents
Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite Download PDFInfo
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- CN1317359C CN1317359C CNB2004100298765A CN200410029876A CN1317359C CN 1317359 C CN1317359 C CN 1317359C CN B2004100298765 A CNB2004100298765 A CN B2004100298765A CN 200410029876 A CN200410029876 A CN 200410029876A CN 1317359 C CN1317359 C CN 1317359C
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- Prior art keywords
- zeolite
- heavy
- ammonium
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- rare
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- 239000010457 zeolite Substances 0.000 title claims abstract description 157
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 147
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 62
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 43
- 238000005336 cracking Methods 0.000 title claims abstract description 24
- 239000003209 petroleum derivative Substances 0.000 title claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- -1 rare earth salt Chemical class 0.000 claims abstract description 24
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 12
- 239000004927 clay Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- 238000010009 beating Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000005995 Aluminium silicate Substances 0.000 claims description 22
- 235000012211 aluminium silicate Nutrition 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 235000019270 ammonium chloride Nutrition 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- NDGSBJSAXJUQTE-UHFFFAOYSA-N azane;phosphorous acid Chemical compound N.OP(O)O NDGSBJSAXJUQTE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000003502 gasoline Substances 0.000 abstract description 43
- 239000011259 mixed solution Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000047 product Substances 0.000 description 28
- 239000000126 substance Substances 0.000 description 28
- 239000002002 slurry Substances 0.000 description 27
- 150000001336 alkenes Chemical class 0.000 description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 11
- 238000005660 chlorination reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- VFYUVMGJOFRPRT-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-dimethyl-nonylazanium Chemical compound CCCCCCCCC[N+](C)(C)C1CC(C)(C)N([O])C(C)(C)C1 VFYUVMGJOFRPRT-UHFFFAOYSA-N 0.000 description 5
- 101100219344 Arabidopsis thaliana CAT7 gene Proteins 0.000 description 5
- 101100494447 Arabidopsis thaliana CAT9 gene Proteins 0.000 description 5
- 101150013917 CAT8 gene Proteins 0.000 description 5
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 5
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 5
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 101000643890 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 5 Proteins 0.000 description 4
- 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 4
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 102100029272 5-demethoxyubiquinone hydroxylase, mitochondrial Human genes 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 102100039339 Atrial natriuretic peptide receptor 1 Human genes 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 3
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 3
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 101000770593 Homo sapiens 5-demethoxyubiquinone hydroxylase, mitochondrial Proteins 0.000 description 3
- 101000961044 Homo sapiens Atrial natriuretic peptide receptor 1 Proteins 0.000 description 3
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- 108091006230 SLC7A3 Proteins 0.000 description 3
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- JSOQIZDOEIKRLY-UHFFFAOYSA-N n-propylnitrous amide Chemical compound CCCNN=O JSOQIZDOEIKRLY-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229940095064 tartrate Drugs 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 101100219343 Arabidopsis thaliana CAT6 gene Proteins 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- WZPYNSUXJNGWIJ-UHFFFAOYSA-N azanium 2-carboxy-4-sulfophenolate Chemical compound S(=O)(=O)(O)C1=CC=C(C(C(=O)[O-])=C1)O.[NH4+] WZPYNSUXJNGWIJ-UHFFFAOYSA-N 0.000 description 1
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 1
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a petroleum hydrocarbon cracking catalyst containing Y-type zeolite, clay and an inorganic oxide binding agent. The petroleum hydrocarbon cracking catalyst is characterized in that 30 to 100 wt% of rare earth super stabilized Y-type zeolite is contained in the Y-type zeolite. The preparation method of the rare earth super stabilized Y-type zeolite comprises the step that zeolite is treated with a mixed solution prepared from rare earth salt and citric acid or with a mixed solution prepared from inorganic ammonium salt, rare earth salt and citric acid. The catalyst can effectively reduce the olefine content in catalytically cracked gasoline and obviously improve the yield of light oil.
Description
Technical field
The invention relates to a kind of cracking catalyst for petroleum hydrocarbon, more particularly, is the cracking catalyst for petroleum hydrocarbon that contains extremely steady y-type zeolite of rare earth about a kind of.
Background technology
Along with the specification of quality increasingly stringent of environment protection to gasoline products, gasoline develops into reformulated gasoline from white gasoline.In the standard of reformulated gasoline, require the vapour pressure and the benzene content of restriction gasoline on the one hand, on the other hand, also will progressively limit the content of olefin component.Such as, the olefin(e) centent in world's fuel oil standard in the II class gasoline standard requirement gasoline component is below 20 volume %.China on July 1st, 2002 in Beijing, the gasoline standard carried out of Shanghai, three big cities, Guangzhou, require the olefin(e) centent in the gasoline component to be lower than 35 volume %.China's gasoline quality standard from now on also will further limit the content of olefin component in the gasoline.
Catalytic cracking is to produce one of major technique of motor spirit component, and its gasoline yield can reach more than the 50 heavy %, and catalytic gasoline is the main blend component of motor spirit.In China, catalytic gasoline accounts for more than 80% of motor spirit blend component.Since the 1980s, the unleaded catalytic cracking technology that forces of motor spirit develops to the direction of producing stop bracket gasoline.For this reason, wide variation have taken place in the processing condition of catalytic cracking and catalyst type.At process aspect, mainly be to improve temperature of reaction, shorten the reaction times, improve the reaction severity, suppressed cracking reaction, improve the contact efficiency of riser tube bottom oil gas and catalyzer; Aspect catalyzer, developed USY type zeolite in conjunction with the catalyzer of inert base or active matrix and the composite catalyst of dissimilar zeolites.
Though catalytic cracking technology has been obtained above-mentioned progress, satisfied the requirement of unleaded gasoline, improved the octane value of gasoline, but no matter be by changing processing condition, also being to use the new zeolite catalyzer, all is the octane value that increases gasoline with the olefin(e) centent in the raising gasoline component.At present the olefin(e) centent in the gasoline component is 35～65 heavy %, and this and reformulated gasoline differ greatly to the requirement of olefin(e) centent.
Using the cracking catalyst of high performance reduction content of olefin in gasoline in the catalytic cracking process process is directly to reduce one of both economical, more satisfactory approach of catalytically cracked gasoline product olefin(e) centent.
U.S. Grace Davison company has reported that in american petroleum NPRA (NPRA) in 1998 annual meeting trade names are industrial application data (the NPRA Annual Mtg. of the catalyzer of RFG, 1998, AM-98-11), guaranteeing to reduce alkene 5～10v% under the condition that product distributes.Akzo NobleCatalysts company has reported the industrial application data of olefine lowering catalyst in Japanese Kashima Oil company in American Chemical Society (ACS) in 1999 annual meeting, report declares that its catalyzer that reduces alkene is under the condition that guarantees product distribution and gasoline octane rating, can reduce gasoline olefin 8v% (ACS PREPRINTS, 43 (3) 1999,515).Consider that for coml these concrete technical intelligence that reduce gasoline olefin activity of such catalysts constituent element there is no the play-by-play of document.
We know that the key that reduces the content of olefin in gasoline catalyst technology is that exploitation hydrogen transference ability is strong, can effectively reduce content of olefin in gasoline, also has the y-type zeolite active ingredient of good coke selectivity and products distribution simultaneously.
USP4 discloses a kind of y-type zeolite and preparation method of ultra high silicon content in 093,560.Relate in its preparation method ammonium salt with a kind of EDTA/or an alkali metal salt and a kind of mineral acid handle a kind of SiO
2/ Al
2O
3NH than 2～6
4 +Type or alkali metal type Y zeolite carry out framework dealumination, and then carry out rare earth or other ion-exchange as required, and this preparation method's purpose is the Al that removes in the y-type zeolite skeleton.
USP5 discloses a kind of treatment process of y-type zeolite in 143,878.Mention in this method with a kind of organic acid and further handle a kind of NH through dealuminzation
4 +The Y zeolite of type, H type or metal ion exchanged carries out framework dealumination, and the lattice constant of gained target product y-type zeolite obviously, as the active component of cracking catalyst, can not reduce the olefin(e) centent of catalytic gasoline effectively between 2.423～2.433nm.
USP5 discloses a kind of dealuminium Y type beta stone and preparation method of ultralow lattice constant in 534,135.Relate in its preparation method and adopt a kind of acid further to handle a kind of ultrastable Y through the high temperature hydrothermal dealumination, carry out degree of depth framework dealumination, the lattice constant of gained target product is lower than 2.419nm, obviously, as the active component of cracking catalyst, can not reduce the olefin(e) centent of catalytic gasoline effectively.
USP5 discloses a kind of nondestructive ground has carried out the Tricationic exchange to molecular screen material method in 292,697.This method is to contain the Tricationic that comprises aluminium and rare earth and ion exchanged soln and a kind of molecular screen material of y-type zeolite that comprises of Tricationic complexing agent carries out ion-exchange with a kind of.Related Tricationic complexing agent comprise alpha-hydroxy carboxylic acid compounds, beta-hydroxycarboxylic acids, γ-hydroxycarboxylic acid, alpha-amino carboxylic acid, beta-amino carboxylic acid, γ ,-aminocarboxylic acid, lactic acid, tartrate, Padil and 15-crown ether, the pH scope of said ion exchanged soln is 4～8, under this pH value condition, can not remove the non-framework aluminum of zeolite.
USP4 discloses a kind of rare earth-stabilized dealuminium Y type beta stone and preparation method thereof in 701,431.Its preparation method is that a kind of ammonium type or alkali metal ion type Y zeolite are contacted with a kind of dealuminzation reagent, so that remove the framework aluminum more than at least 5%, carries out rare earth ion exchanged then, its objective is and carries out framework dealumination, improves the framework si-al ratio of zeolite.
A kind of preparation method of type-Y high silicon zeolite is disclosed among the CN 1065253A.This method comprises: (1) carries out chemical dealuminization with a kind of dealumination agent with the NaY zeolite in ammonium sulfate solution, filter, washing, said dealumination agent comprises oxalic acid, sulphosalicylic acid, oxalic acid+sulfuric acid, ammonium oxalate+sulfuric acid, ammonium oxalate+hydrochloric acid, ammonium silicofluoride or ammonium borofluoride; (2) filter cake is carried out hydrothermal treatment consists at 400～700 ℃; (3) use the method identical with step (1) to carry out chemical dealuminization again one time step (2) products therefrom, this method is with zeolite framework aluminium deep removal.
A kind of preparation method of type-Y high silicon zeolite is disclosed among the CN 1058358A.This method is with NaY or NH
4The NaY zeolite carries out chemical dealuminization in the presence of complexing agent and quantitative acid, said acid is that H can be provided
+Inorganic or organic acid, comprise hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, acetic acid, oxalic acid, yellow basic Whitfield's ointment, tartrate, citric acid etc., said complexing agent be can and Al
3+The ion of complexing, salt or organism comprise ammonium oxalate (sodium), sulphosalicylic acid ammonium (sodium), fluorion, ammonium tartrate (sodium), citric acid ammonium (sodium), methyl ethyl diketone etc.Can add Si (OH) in the chemical dealuminization reaction process
4, V (OH)
4 +, B (OH)
4 -, Ti (OH)
4, Ga (OH)
4 -, Ga (OH)
4 -, Fe (OH)
4 -Deng high price metal or nonmetal hydrated ion, make its metal or nonmetallic ion mend hole into the zeolite dealuminzation.Zeolite through chemical dealuminization carries out hydrothermal treatment consists again under 500～800 ℃ of temperature.The purpose of this method also is with zeolite framework aluminium deep removal.
A kind of method to the ultrastable Y modification is disclosed among the CN 1288858A.This method is ultrastable Y to be carried out the dealuminzation modification with complexing agents such as citric acid, tartrate or oxalic acid handle.The purpose of this method also is the deep removal of zeolite framework aluminium.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of cracking catalyst for petroleum hydrocarbon that contains extremely steady y-type zeolite of rare earth, this catalyzer can reduce the olefin(e) centent in the pressure gasoline effectively, obviously increases catalytic cracking lightweight oil product yield.
Catalyst for cracking petroleum hydrocarbons provided by the present invention is by butt weight, the y-type zeolite that contains 10～50 heavy %, 0～5 heavy % selects the shape zeolite, the clay of 0～70 heavy %, and the inorganic oxide binder of surplus, it is characterized in that in the said y-type zeolite that contain a kind of extremely steady y-type zeolite of rare earth of 30～100 heavy %, this zeolite is prepared by following step:
(1) the NaY zeolite is carried out ion-exchange with inorganic ammonium salt solution, make the Na of zeolite
2O content is 1～6 heavy %, then under 100% steam atmosphere in 450～750 ℃ of roastings 0.5～10 hour;
(2) (1) products therefrom is mixed with deionized water the making beating and be warming up to 50～100 ℃, add a kind of mixing solutions or a kind of mixing solutions of forming by rare-earth salts and citric acid of forming by inorganic ammonium salt, rare-earth salts and citric acid, stir, filter, wash, make RE in the zeolite
2O
3Content is 0.5～7 heavy %, Na
2O content is lower than 2.0 heavy %;
(3) with (2) products therefrom under air or 100% steam atmosphere in 450～750 ℃ of roastings 0.5～4 hour.
In the catalyzer provided by the invention, said a kind of extremely steady y-type zeolite of rare earth, rare earth is with RE
2O
3Meter, its content are 0.5～7 heavy %, preferred 2～6 heavy %, Na
2O content is lower than 2.0 heavy %, the lattice constant (a of zeolite
0) be 2.450～2.460nm; In the preparation process of this extremely steady y-type zeolite of rare earth, the said ion-exchange of step (1) is carried out according to the prior art condition, be that those of ordinary skill in the art is known, here no longer numerous stating, condition commonly used is that temperature is room temperature～100 ℃, be preferably 50～95 ℃, the time is more than 10 minutes, is preferably 0.5～2 hour; The consumption of inorganic ammonium salt is to exchange the Na of back products therefrom
2O content is standard in said scope.Preferred 500～650 ℃ of said maturing temperature, roasting time is 1～3 hour.
Catalyzer provided by the invention, in the preparation process of said a kind of extremely steady y-type zeolite of rare earth, the said rare-earth salts of step (2) is meant the rare-earth salts that is used for the zeolite rare earth exchanged well known to those skilled in the art, generally is to be muriate, nitrate or the vitriol of main ingredient with lanthanum and/or cerium; Wherein the content of lanthanum and/or cerium (in oxide compound) is preferably greater than 60 heavy % greater than 50 heavy %, more preferably greater than 70 heavy %.The weight ratio of said zeolite and rare-earth salts, citric acid is 1: (0.005～0.08): (0.01～0.20), and preferred 1: (0.02～0.07): (0.04～0.16), wherein rare-earth salts is in oxide compound, and citric acid is with C
6H
8O
7H
2The O meter.Said above-mentioned two kinds of mixing solutionss, preferably 10～120 minutes, more preferably join in the slurries of zeolite in time of 15～60 minutes, mix then stir 0.2～10 hour, be preferably 0.5～4 hour.
Catalyzer provided by the invention, in the preparation process of said a kind of extremely steady y-type zeolite of rare earth, said inorganic ammonium salt comprises one or more in the inorganic ammonium salt of ammonium chloride, ammonium sulfate, ammonium nitrate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium, ammonium acetate, ammonium formiate etc. in step (1) and (2).The effect of this inorganic ammonium salt is the Na that ammonium ion exchange reduces zeolite
2O content, its consumption basis is to zeolite Na
2The requirement of O content and deciding.
Catalyzer provided by the invention, among the preparation method of said a kind of extremely steady y-type zeolite of rare earth, said maturing temperature of step (3) and roasting time are with the lattice constant (a of products therefrom
0) in said scope standard, preferred maturing temperature is 450～650 ℃, roasting time is for being 1～3 hour.
Catalyzer provided by the invention, said a kind of extremely steady y-type zeolite of rare earth, the mixing solutions of employing rare-earth salts and citric acid carries out rare earth exchanged simultaneously and the complexing dealumination reaction obtains, on the one hand, acidity and Al that this complexing mixing solutions is suitable
3+When complex ability is guaranteed very high zeolite rare earth exchanged efficient, can also remove the non-skeleton Al of zeolite effectively
2O
3, expand the secondary duct, improve the accessibility in zeolite catalysis active centre, increase zeolite product specific surface area, improve degree of crystallinity; On the other hand, the molecular dimension that the mixture of rare-earth salts and citric acid is suitable makes it but seldom remove the framework aluminum of zeolite when removing outer surface of zeolite and non-framework aluminum effectively, thereby not causing the reduction of zeolite product lattice constant, this is just for the desired effect that obtains of the purpose that reduces the pressure gasoline olefin(e) centent.
Catalyzer provided by the invention, described y-type zeolite, except the extremely steady y-type zeolite of rare earth of preceding method preparation accounts for 30～100 heavy %, 0～70% other y-type zeolite that contains in addition is the various y-type zeolites that generally adopt in the prior art, y-type zeolite such as Hydrogen, ammonium type or rare-earth type, perhaps through the y-type zeolite of Hydrogen, ammonium type or the rare-earth type of phosphorus modification, or through the y-type zeolite of alkali-earth metal modified Hydrogen, ammonium type or rare-earth type, the perhaps ultrastable Y of handling through super stabilizing, or the combination of several above zeolites.
Catalyzer provided by the invention, said select the shape zeolite be generally adopt in the prior art comprise ZSM-5, ZRP, β zeolite select the shape zeolite, can be Hydrogen or ammonium type, also can be through element modified.
Said selecting in the shape zeolite, ZSM-5 zeolite are the exploitations of early seventies U.S. Mobil company, are typical case's representatives of five-membered ring structure high-silicon zeolite, have unique pore passage structure.ZRP is the five-ring supersiliceous zeolite that contains rare earth, USP5, and 232,675 disclose its preparation method, and CN1093101A has disclosed the ZSM-5 zeolite (P-ZRP) of introducing rare earth and phosphorus, handles the ZRP zeolite with aluminum phosphate and obtains.The said shape zeolite of selecting also can be through transition metal, phosphorus, rare earth element or alkali earth metal modifications such as Zn, Mn, Ti, Zr, Cr, Ni, Cu, Fe, Co.
Cracking catalyst for petroleum hydrocarbon provided by the present invention, said clay are the combination that generally adopt in the prior art various comprise one or more clay materials in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, the tired clay material that takes off stone etc.
Cracking catalyst for petroleum hydrocarbon provided by the present invention, described inorganic oxide binder is one or more the mixture in pseudo-boehmite, aluminium colloidal sol, silicon sol, silicon-aluminum sol and the aluminum phosphate colloidal sol that generally adopts in the prior art, wherein preferred pseudo-boehmite, aluminium colloidal sol or silicon sol.
Cracking catalyst for petroleum hydrocarbon provided by the invention, because part or all of active ingredient has wherein adopted a kind of extremely steady y-type zeolite of rare earth of peculiar methods preparation, therefore both had the performance of good reduction catalytically cracked gasoline product olefin(e) centent, have good heavy oil cracking ability and coke selectivity again, can obviously increase the yield of catalytic cracking lightweight oil product.
Embodiment
The following examples will give further instruction to the present invention, but be not therefore and restriction the present invention.
The Na of prepared zeolite among each embodiment and the comparative example
2O content is by aas determination; RE
2O
3, Al
2O
3And SiO
2Content is by x-ray fluorescence spectrometry; Lattice constant and relative crystallinity by X-ray diffraction method (XRD) adopt RIPP 145-90 standard method (see " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety version) measure; Specific surface area, pore volume are measured by standard BET method.
Comparative Examples 1
This Comparative Examples illustrates that commercial run prepares the hyperastable Y-type RE zeolite routinely.
Get the NaHY zeolite M and the making beating of 1200 milliliters of decationized Y sieve water of preparation among 100 gram (butt) embodiment 1, (production of Inner Mongol Baotou rare earth factory contains 5.36 and restrains RE to add 100 milliliters of chlorination mixed rare earth solutions in the slurries
2O
3, RE
2O
3Consist of La
2O
353.2%, CeO
213.0%, Pr
6O
1113.0%, Nd
2O
320.8%), is warming up to 90 ℃, and reacted with this understanding 45 minutes, filter, washing,, make hyperastable Y-type RE zeolite contrast sample, be numbered DB1 filter cake roasting 2 hours in 600 ℃ of air.
The chemical constitution of DB1 sees Table 1, and main physical and chemical performance sees Table 2.
Comparative Examples 2
This Comparative Examples prepares the process of extremely steady y-type zeolite of rare earth again for preparing overstable gamma zeolite according to the method that CN1288858A provided with rare earth exchanged.
Get 100 gram (butt) NaHY zeolite M and 1200 milliliters of decationized Y sieve water making beating, in slurries, add 100 milliliters of ammonium chloride solutions (containing 30 gram ammonium chlorides), be warming up to 90 ℃, and reacted with this understanding 45 minutes, filter, wash, with filter cake roasting 2 hours in 600 ℃ of air, make overstable gamma zeolite (USY).
With gained USY and the making beating of 1200 milliliters of decationized Y sieve water, be warming up to 90 ℃, add 100 milliliters of citric acid solutions with the speed of 1 ml/min in the slurries then and (contain 20 and restrain C
6H
8O
7H
2O), and reacted with this understanding 4 hours, filter, wash, exchange under 80～90 ℃ with the chlorination mixed rare earth solution again, make overstable gamma zeolite contrast sample, be numbered DB2.
The chemical constitution of DB2 sees Table 1, and main physical and chemical performance sees Table 2.
Comparative Examples 3
This Comparative Examples is according to USP4, and 701,431 methods that provided prepare rare earth-stabilized dealuminium Y type beta stone.
In 1200 milliliters of decationized Y sieve water, add 18 milliliters of concentrated hydrochloric acid (analytical pure, concentration is 36%), add 100 gram (butt) NaHY zeolite M making beating again, be warming up to 90 ℃ and reacted 2 hours, add 100 milliliters of chlorination mixed rare earth solutions in the slurries then and (contain 7.5 and restrain RE
2O
3), and continue reaction 45 minutes, filter, washing, with filter cake roasting 2 hours in 600 ℃ of air, make rare earth-stabilized dealuminium Y type beta stone contrast sample, be numbered DB3.
The chemical constitution of DB3 sees Table 1, and main physical and chemical performance sees Table 2.
The preparation process of said extremely steady y-type zeolite of rare earth in embodiment 1～7 explanation catalyzer provided by the invention.
Embodiment 1
In stirring tank, add 60 kilograms of decationized Y sieve water, 3 kilograms of NH
4(Qilu Petrochemical company catalyst plant is produced, Na for Cl and 3 kilograms of (butt) NaY zeolites
2The heavy % of O14, lattice constant 2.465nm), carried out ion-exchange 45 minutes in 90 ℃, filter, washing,, make a roasting NaHY zeolite M filter cake roasting 2 hours under 600 ℃, 100% water vapor.It consists of Na
2O5.5 heavy %, Al
2O
323.4 heavy %, SiO
2The heavy % of %69.7, lattice constant 2.455nm, relative crystallinity 78.2%.
Get 100 gram (butt) NaHY zeolite M and the making beating of 1200 milliliters of decationized Y sieve water, be warming up to 90 ℃, (contain 4 and restrain C with the speed of the 5 ml/min mixing solutions of 100 milliliters of chlorination mishmetals of adding and citric acid in the slurries then
6H
8O
7H
2O and 5.36 gram RE
2O
3), and reacted with this understanding 45 minutes, filter, washing, with filter cake roasting 2 hours in 600 ℃ of air, make extremely steady y-type zeolite of rare earth, be numbered A.
The chemical constitution of A sees Table 1, and main physical and chemical performance sees Table 2.
Embodiment 2
The preparation method is with example 1, contains 8 gram C in the mixing solutions of different is 100 milliliters of chlorination mishmetals and citric acid
6H
8O
7H
2O makes extremely steady y-type zeolite of rare earth, is numbered B.
The chemical constitution of B sees Table 1, and main physical and chemical performance sees Table 2.
Embodiment 3
The preparation method is with example 1, contains 12 gram C in the mixing solutions of different is 100 milliliters of chlorination mishmetals and citric acid
6H
8O
7H
2O makes the hyperastable Y-type RE zeolite, is numbered C.
The chemical constitution of C sees Table 1, and main physical and chemical performance sees Table 2.
Embodiment 4
The preparation method is with example 1, contains 16 gram C in the mixing solutions of different is 100 milliliters of chlorination mishmetals and citric acid
6H
8O
7H
2O makes the hyperastable Y-type RE zeolite, is numbered D.
The chemical constitution of D sees Table 1, and main physical and chemical performance sees Table 2.
Embodiment 5
The preparation method is with example 1, and the mixing solutions that different is with 100 milliliters of ammonium chlorides, chlorination mishmetal and citric acid (contains 10 gram ammonium chlorides, 3.5 gram RE
2O
3With 8 gram C
6H
8O
7H
2O), make the hyperastable Y-type RE zeolite, be numbered E.
The chemical constitution of E sees Table 1, and main physical and chemical performance sees Table 2.
Embodiment 6
The preparation method is with example 1, and the mixing solutions that different is with 100 milliliters of ammonium chlorides, chlorination mishmetal and citric acid (contains 15 gram ammonium chlorides, 2.0 gram RE
2O
3With 8 gram C
6H
8O
7H
2O), make the hyperastable Y-type RE zeolite, be numbered F.
The chemical constitution of F sees Table 1, and main physical and chemical performance sees Table 2.
Embodiment 7
The preparation method is with example 1, and different is (to contain 6.5 gram RE with 100 milliliters the chlorination mishmetal and the mixing solutions of citric acid
2O
3With 8 gram C
6H
8O
7H
2O), make the hyperastable Y-type RE zeolite, be numbered G.
The chemical constitution of G sees Table 1, and main physical and chemical performance sees Table 2.
Table 1
| The embodiment numbering | The zeolite numbering | Chemical constitution/m% | |||
| Na 2O | RE 2O 3 | Al 2O 3 | SiO 2 | ||
| Comparative Examples 1 | DB1 | 2.3 | 4.86 | 23.6 | 67.9 |
| Comparative Examples 2 | DB2 | 0.35 | 4.0 | 14.3 | 83.1 |
| Comparative Examples 3 | DB3 | 0.60 | 7.2 | 16.0 | 76.0 |
| Embodiment 1 | A | 1.8 | 4.88 | 21.4 | 69.4 |
| Embodiment 2 | B | 1.6 | 4.76 | 20.7 | 71.1 |
| Embodiment 3 | C | 1.3 | 4.77 | 19.0 | 72.3 |
| Embodiment 4 | D | 1.0 | 4.6 | 18.4 | 74.1 |
| Embodiment 5 | E | 1.1 | 3.2 | 20.9 | 72.7 |
| Embodiment 6 | F | 1.2 | 1.8 | 20.5 | 75.7 |
| Embodiment 7 | G | 1.2 | 6.0 | 19.2 | 72.8 |
Table 2
| The embodiment numbering | The zeolite numbering | Physical and chemical performance | |||
| a 0 | I/I 0 | Specific surface | Pore volume | ||
| nm | ％ | m 2/g | ml/g | ||
| Comparative Examples 1 | DB1 | 2.456 | 60.4 | 593 | 0.316 |
| Comparative Examples 2 | DB2 | 2.440 | 73.4 | 702 | 0.381 |
| Comparative Examples 3 | DB3 | 2.450 | 58.2 | 632 | 0.350 |
| Embodiment 1 | A | 2.456 | 63.9 | 616 | 0.333 |
| Embodiment 2 | B | 2.456 | 65.3 | 666 | 0.359 |
| Embodiment 3 | C | 2.455 | 66.7 | 684 | 0.370 |
| Embodiment 4 | D | 2.454 | 65.0 | 673 | 0.367 |
| Embodiment 5 | E | 2.454 | 66.3 | 680 | 0.371 |
| Embodiment 6 | F | 2.453 | 68.5 | 685 | 0.375 |
| Embodiment 7 | G | 2.458 | 63.6 | 656 | 0.350 |
As can be seen from Table 2, the hyperastable Y-type RE zeolite that adopts in the catalyzer of the present invention can optionally remove the non-skeleton Al of zeolite
2O
3, expand the secondary duct, improve accessibility, increase specific surface area, improve degree of crystallinity, and do not reduce the lattice constant of zeolite product, do not influence the rare earth exchanged rate and the Na of zeolite yet
2The O decreasing ratio.
Following examples illustrate Preparation of catalysts process provided by the invention.
Embodiment 8
Get 162.2 gram (butt) kaolin (kaolin company in Suzhou produces, solid content 78 heavy %), add 750 gram decationized Y sieve water making beating 90 minutes, add 54 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Add concentration and be 11 milliliters of the hydrochloric acid of 36 heavy %, after stirring, be warming up to 60 ℃ and aging 1 hour.To contain 126 gram (butt) modified RE overstable gamma zeolite A, the zeolite slurry of solid content 30 heavy %, 83.8 gram aluminium colloidal sols (the Qilu Petrochemical catalyst plant is produced, solid content 21.5 heavy %) join in the said mixture, after making beating mixes.With slurries in 120 ℃ of oven dry, 400 ℃ of roastings 1 hour.Get 80～120 order products therefroms 100 grams (butt) and add 1000 milliliters in decationized Y sieve water and 3 gram ammonium chlorides, regulate slurries pH value to 3.0 with the hydrochloric acid of 2 heavy %, stirring is warming up to 60 ℃, washs 30 minutes after-filtration, drying, makes catalyzer CAT1.
Catalyzer CAT1 contains 35 heavy % hyperastable Y-type RE zeolite A, 45 heavy % kaolin and 20 heavy %Al
2O
3.
Embodiment 9～14
Preparation process is with embodiment 8, and its difference is to replace zeolite A with zeolite B, C, D, E, F, G respectively, makes catalyzer CAT2, CAT3, CAT4, CAT5, CAT6, CAT7 successively.
Catalyzer CAT2, CAT3, CAT4, CAT5, CAT6, CAT7 contain hyperastable Y-type RE zeolite B, C, D, E, F, the G of 35 heavy % respectively, and 45 heavy % kaolin and 20 heavy %Al
2O
3
Comparative Examples 4～6
The preparation method is with embodiment 8, and different is with replacing hyperastable Y-type RE zeolite A with contrast zeolite DB1, DB2, DB3 respectively, making comparative catalyst DBJ1, DBJ2, DBJ3 successively.
Comparative catalyst DBJ1, DBJ2, DBJ3 contain 35 heavy %DB1, DB2, DB3 respectively, and 45 heavy % kaolin and 20 heavy %Al
2O
3
Embodiment 15
The catalytic performance of present embodiment explanation cracking catalyst CAT1～CAT7.
80～120 purpose catalyzer CAT1～CAT7 through 800 ℃, 100% steam aging 12 hours, are estimated on heavy oil microreactor then.Stock oil character sees Table 3.Evaluation result sees Table 4.
Comparative Examples 7
The catalytic performance of this Comparative Examples explanation comparative catalyst DBJ1～DBJ3.
80～120 purpose comparative catalyst DBJ1～DBJ3 through 800 ℃, 100% steam aging 12 hours, are estimated on heavy oil microreactor then.Evaluation result sees Table 5.
Table 3
| Density (20 ℃), g/cm 3Viscosity (100 ℃), mm 2/ s zero pour, ℃ carbon residue, m% | 0.9154 6.962 35 0.18 |
| Elementary composition, m% C H S N | 85.38 12.03 2.0 0.16 |
| Four components, m% stable hydrocarbon aromatic hydrocarbons gum asphalt | 64.0 32.0 4.0 0.0 |
| Boiling range, ℃ IBP/5% 10%/30% 50%/70% 90%/95% | 329/363 378/410 436/462 501/518 |
Table 4
| The catalyzer numbering | CAT1 | CAT2 | CAT3 | CAT4 | CAT5 | CAT6 | CAT7 |
| The zeolite numbering | A | B | C | D | E | F | G |
| MAT/12h | 62 | 63 | 68 | 65 | 62 | 60 | 68 |
| Reaction conditions | 482 ℃ of temperature, agent-oil ratio 4, air speed 16h -1 | ||||||
| Productive rate, m% gas C 5Gasoline, diesel heavy oil coke | 9.7 55.3 19.4 13.0 2.6 | 14.4 56.7 18.2 8.4 2.3 | 14.4 56.6 18.3 8.2 2.5 | 14.8 58.1 17.4 7.4 2.3 | 10.9 55.4 19.2 12.2 2.3 | 10.9 56.5 18.5 11.9 2.2 | 13.7 57.9 17.9 7.9 2.6 |
| Transformation efficiency, m% | 67.6 | 73.4 | 73.5 | 75.2 | 68.6 | 69.6 | 74.2 |
| Light oil, m% | 74.7 | 74.9 | 74.9 | 75.5 | 74.6 | 75.0 | 75.8 |
| Gasoline is formed N-alkanes isomeric alkane alkene naphthenic hydrocarbon aromatic hydrocarbons | 3.62 38.40 21.20 9.44 27.26 | 3.67 38.10 19.23 8.79 30.09 | 3.57 38.39 18.68 8.60 30.18 | 3.64 38.55 18.50 8.73 30.45 | 3.74 37.83 21.11 9.14 28.09 | 3.55 37.99 21.21 9.63 27.46 | 3.93 39.91 16.19 8.62 31.23 |
Table 5
| Catalyzer | DBJ1 | DBJ2 | DBJ3 |
| Zeolite | DB1 | DB2 | DB3 |
| MAT/12h | 61 | 60 | 64 |
| Reaction conditions | 482 ℃ of temperature, agent-oil ratio 4, air speed 16h -1 | ||
| Productive rate, m% gas C 5Gasoline, diesel heavy oil coke | 12.1 53.5 18.1 13.8 2.5 | 14.0 50.8 20.0 13.7 1.5 | 16.3 56.6 17.1 8.1 2.7 |
| Transformation efficiency, m% | 68.1 | 66.3 | 74.8 |
| Light oil, m% | 71.6 | 70.8 | 73.7 |
| Gasoline is formed N-alkanes isomeric alkane alkene naphthenic hydrocarbon aromatic hydrocarbons | 3.75 36.04 22.21 9.16 28.74 | 3.43 33.14 30.75 9.49 22.99 | 3.48 30.79 25.07 8.86 31.72 |
From table 4, table 5 as can be seen, compare with the comparative catalyst, the hyperastable Y-type RE zeolite of employing the inventive method preparation not only has good heavy oil cracking performance and coke selectivity as the cracking catalyst of active ingredient, and can also reduce the olefin(e) centent of catalytically cracked gasoline product effectively, and obviously increase yield of light oil.
Embodiment 16
Get 234 gram (butt) pseudo-boehmites, add 1288 gram decationized Y sieve water making beating 30 minutes, after adding 47 ml concns and being the hcl acidifying of 36 heavy %, after continuing to stir 45, be warming up to 60 ℃ and aging 1 hour.To contain 126 gram (butt) modified RE overstable gamma zeolite B, the zeolite slurry of solid content 30 heavy % joins in the said mixture, and making beating mixes.With slurries in 120 ℃ of oven dry, 400 ℃ of roastings 1 hour.Get 80～120 order products therefroms 100 grams (butt) and add 1000 milliliters in decationized Y sieve water and 3 gram ammonium chlorides, regulate slurries pH value to 3.0 with the hydrochloric acid of 2 heavy %, stirring is warming up to 60 ℃, washs 30 minutes after-filtration, drying, makes catalyzer CAT8.
Catalyzer CAT8 consists of: 35 heavy % hyperastable Y-type RE zeolite B and 65 heavy %Al
2O
3
Embodiment 17
Get 144 gram (butt) kaolin (kaolin company in Suzhou produces, solid content 78 heavy %), (the Qilu Petrochemical catalyst plant is produced, SiO to add 62.28 gram water glass
2Content 28.9 heavy %, Na
2O content 8.9%) and 700 gram decationized Y sieve water making beating 90 minutes, add 36 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Add concentration and be 30 milliliters of the hydrochloric acid of 36 heavy %, after stirring, be warming up to 60 ℃ and aging 1 hour.To contain 126 gram (butt) modified RE overstable gamma zeolite B, the zeolite slurry of solid content 30 heavy %, 167.4 gram aluminium colloidal sols (the Qilu Petrochemical catalyst plant is produced, solid content 21.5 heavy %) join in the said mixture, after making beating mixes.With slurries in 120 ℃ of oven dry, 400 ℃ of roastings 1 hour.Get 80～120 order products therefroms 100 grams (butt) and add 1000 milliliters in decationized Y sieve water and 3 gram ammonium chlorides, regulate slurries pH value to 3.0 with the hydrochloric acid of 2 heavy %, stirring is warming up to 60 ℃, washs 30 minutes after-filtration, drying, makes catalyzer CAT9.
Catalyzer CAT9 consists of: 35 heavy % hyperastable Y-type RE zeolite B, 40 heavy % kaolin, 5 heavy %SiO
2With 20 heavy %Al
2O
3
Embodiment 18
Get 144 gram (butt) kaolin (kaolin company in Suzhou produces, solid content 78 heavy %), add 750 gram decationized Y sieve water making beating 90 minutes, add 54 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Add concentration and be 11 milliliters of the hydrochloric acid of 36 heavy %, after stirring, be warming up to 60 ℃ and aging 1 hour.Y-type zeolite W (Qilu Petrochemical company catalyst plant product, silica alumina ratio 5.5, the P that will contain 72 gram (butt) modified RE overstable gamma zeolite A and the phosphorous and rare earth of 72 grams (butt)
2O
52.0, RE
2O
38.2, down with), the zeolite slurry of solid content 30 heavy %, 83.8 gram aluminium colloidal sols (the Qilu Petrochemical catalyst plant is produced, solid content 21.5 heavy %) join in the said mixture, after making beating mixes.With slurries in 120 ℃ of oven dry, 400 ℃ of roastings 1 hour.Get 80～120 order products therefroms 100 grams (butt) and add 1000 milliliters in decationized Y sieve water and 3 gram ammonium chlorides, regulate slurries pH value to 3.0 with the hydrochloric acid of 2 heavy %, stirring is warming up to 60 ℃, washs 30 minutes after-filtration, drying, makes catalyzer CAT10.
Catalyzer CAT10 consists of: 20 heavy % hyperastable Y-type RE zeolite B, 20 heavy %W zeolites, 40 heavy % kaolin and 20 heavy %Al
2O
3
Comparative Examples 8
Get 144 gram (butt) kaolin (kaolin company in Suzhou produces, solid content 78 heavy %), add 750 gram decationized Y sieve water making beating 90 minutes, add 54 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Add concentration and be 11 milliliters of the hydrochloric acid of 36 heavy %, after stirring, be warming up to 60 ℃ and aging 1 hour.The y-type zeolite W that will contain the phosphorous and rare earth of 144 grams (butt), the zeolite slurry of solid content 30 heavy %, 83.8 gram aluminium colloidal sols (the Qilu Petrochemical catalyst plant is produced, solid content 21.5 heavy %) join in the said mixture, after making beating mixes.With slurries in 120 ℃ of oven dry, 400 ℃ of roastings 1 hour.Get 80～120 order products therefroms 100 grams (butt) and add 1000 milliliters in decationized Y sieve water and 3 gram ammonium chlorides, regulate slurries pH value to 3.0 with the hydrochloric acid of 2 heavy %, stirring is warming up to 60 ℃, washs 30 minutes after-filtration, drying, makes catalyzer DBJ4.
Catalyzer DBJ4 consists of: 40 heavy % zeolite W, 40 heavy % kaolin and 20 heavy %Al
2O
3
Embodiment 19
Get 154.8 gram (butt) kaolin (kaolin company in Suzhou produces, solid content 78 heavy %), add 750 gram decationized Y sieve water making beating 90 minutes, add 54 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Add concentration and be 11 milliliters of the hydrochloric acid of 36 heavy %, after stirring, be warming up to 60 ℃ and aging 1 hour.(the Qilu Petrochemical catalyst plant is produced will to contain 126 gram (butt) modified RE overstable gamma zeolite B and 7.2 gram (butt) ZRP-5 zeolites, silica alumina ratio 50), the zeolite slurry of solid content 30 heavy %, 83.8 gram aluminium colloidal sols (Qilu Petrochemical catalyst plant productions, solid content 21.5 heavy %) join in the said mixture, after making beating mixes.With slurries in 120 ℃ of oven dry, 400 ℃ of roastings 1 hour.Get 80～120 order products therefroms 100 grams (butt) and add 1000 milliliters in decationized Y sieve water and 3 gram ammonium chlorides, regulate slurries pH value to 3.0 with the hydrochloric acid of 2 heavy %, stirring is warming up to 60 ℃, washs 30 minutes after-filtration, drying, makes catalyzer CAT11.
Catalyzer CAT11 consists of: 35 heavy % hyperastable Y-type RE zeolite B, 2 heavy %ZRP-5 zeolites, 43 heavy % kaolin and 20 heavy %Al
2O
3
Comparative Examples 9
Get 154.8 gram (butt) kaolin (kaolin company in Suzhou produces, solid content 78 heavy %), add 750 gram decationized Y sieve water making beating 90 minutes, add 54 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Add concentration and be 11 milliliters of the hydrochloric acid of 36 heavy %, after stirring, be warming up to 60 ℃ and aging 1 hour.To contain 126 grams (butt) y-type zeolite W and 7.2 phosphorous and rare earth and restrain (the Qilu Petrochemical catalyst plant production of (butt) ZRP-5 zeolites, silica alumina ratio 50), the zeolite slurry of solid content 30 heavy %, 83.8 gram aluminium colloidal sols (Qilu Petrochemical catalyst plant productions, solid content 21.5 heavy %) join in the said mixture, after making beating mixes.With slurries in 120 ℃ of oven dry, 400 ℃ of roastings 1 hour.Get 80～120 order products therefroms 100 grams (butt) and add 1000 milliliters in decationized Y sieve water and 3 gram ammonium chlorides, regulate slurries pH value to 3.0 with the hydrochloric acid of 2 heavy %, stirring is warming up to 60 ℃, washs 30 minutes after-filtration, drying, makes catalyzer DBJ5.
Catalyzer DBJ5 consists of: 35 heavy % zeolite W, 2 heavy %ZRP-5 zeolites, 43 heavy % kaolin and 20 heavy %Al
2O
3
Embodiment 20
The catalytic performance of present embodiment explanation cracking catalyst CAT8 and CAT9.
80～120 purpose catalyzer CAT8 and CAT9 through 800 ℃, 100% steam aging 12 hours, are estimated on heavy oil microreactor then.Stock oil character sees Table 3.Evaluation result sees Table 6.
Comparative Examples 10
The catalytic performance of present embodiment explanation cracking catalyst DBJ4 and DBJ5.
80～120 purpose comparative catalyst DBJ4 and DBJ5 through 800 ℃, 100% steam aging 12 hours, are estimated on heavy oil microreactor then.Stock oil character sees Table 3.Evaluation result sees Table 6.
Table 6
| Example number | Embodiment 18 | Comparative Examples 8 | Embodiment 19 | Comparative Examples 9 |
| Catalyzer | CAT8 | DBJ4 | CAT9 | DBJ5 |
| Zeolite | 20％B+20％W | 40％W | 2％ZRP-5+ 35％B | 2％ZRP-5+ 35％W |
| MAT/12h | 65 | 67 | 65 | 66 |
| Reaction conditions | 482 ℃ of agent-oil ratios of temperature, 4 air speed 16h -1 | |||
| Productive rate, m% gas C 5Gasoline, diesel heavy oil coke | 12.7 57.3 17.2 10.1 2.7 | 13.9 55.8 16.2 11.0 3.1 | 14.7 54.1 18.4 10.5 2.3 | 15.2 54.8 16.5 10.9 2.6 |
| Transformation efficiency, m% | 72.7 | 72.8 | 71.1 | 72.6 |
| Light oil, m% | 74.5 | 72.0 | 72.5 | 71.3 |
| Gasoline is formed N-alkanes isomeric alkane alkene naphthenic hydrocarbon aromatic hydrocarbons | 3.42 38.35 21.00 9.37 27.86 | 3.21 38.83 20.42 9.02 28.52 | 3.60 37.17 22.20 8.25 28.78 | 3.76 35.94 22.21 9.55 28.54 |
As can be seen from Table 6, compare with the comparative catalyst, adopt cracking catalyst provided by the invention not only to have good heavy oil cracking performance and coke selectivity, and can also reduce the olefin(e) centent of catalytically cracked gasoline product effectively, and obviously increase yield of light oil.
Claims (8)
1. cracking catalyst for petroleum hydrocarbon, by butt weight, the y-type zeolite that contains 10～50 heavy %, 0～5 heavy % selects the shape zeolite, the clay of 0～70 heavy %, and the inorganic oxide binder of surplus is characterized in that in the said y-type zeolite, contain a kind of extremely steady y-type zeolite of rare earth of 30～100 heavy %, this extremely steady y-type zeolite of rare earth is prepared by following process:
(1) the NaY zeolite is carried out ion-exchange with inorganic ammonium salt solution, make the Na of zeolite
2O content is 1～6 heavy %, then under 100% steam atmosphere in 450～750 ℃ of roastings 0.5～10 hour;
(2) (1) products therefrom is mixed with deionized water the making beating and be warming up to 50～100 ℃, add a kind of mixing solutions or a kind of mixing solutions of forming by rare-earth salts and citric acid of forming by inorganic ammonium salt, rare-earth salts and citric acid, stir, filter, wash, make RE in the zeolite
2O
3Content is 0.5～7 heavy %, Na
2O content is lower than 2.0 heavy %, and wherein, the weight ratio of said zeolite and rare-earth salts, citric acid is 1: (0.005～0.08): (0.01～0.20), rare-earth salts are in oxide compound, and citric acid is with C
6H
8O
7H
2The O meter;
(3) with (2) products therefrom under air or 100% steam atmosphere in 450～750 ℃ of roastings 0.5～4 hour.
2. according to the catalyzer of claim 1, the weight ratio of said zeolite and rare-earth salts, citric acid is 1: (0.02～0.07): (0.04～0.16).
3. according to the catalyzer of claim 1, inorganic ammonium salt comprises one or more in the inorganic ammonium salt of ammonium chloride, ammonium sulfate, ammonium nitrate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium, ammonium acetate, ammonium formiate in said step (1) and (2).
4. according to the catalyzer of claim 1, except the extremely steady y-type zeolite of rare earth of said process preparation, other y-type zeolite is selected from the y-type zeolite of Hydrogen, ammonium type or rare-earth type, perhaps be selected from the y-type zeolite of Hydrogen, ammonium type or rare-earth type through the phosphorus modification, or the ultrastable Y of super stabilizing processing, or the combination of several above zeolites.
5. according to the catalyzer of claim 1, the said shape zeolite of selecting is ZSM-5.
6. according to the catalyzer of claim 5, the said shape zeolite of selecting is through phosphorus and/or rare earth modified ZSM-5.
7. according to the catalyzer of claim 1, said clay is selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, the tired mixture that takes off in the stone one or more.
8. according to the catalyzer of claim 1, described inorganic oxide binder is selected from one or more the mixture in pseudo-boehmite, aluminium colloidal sol, silicon sol, silicon-aluminum sol and the aluminum phosphate colloidal sol.
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| CN100421795C (en) * | 2005-10-19 | 2008-10-01 | 中国石油化工股份有限公司 | A catalytic cracking catalyst containing faujasite and its preparation method |
| CN101633507B (en) * | 2008-07-24 | 2011-03-30 | 中国石油化工股份有限公司石油化工科学研究院 | A kind of ammonium ion exchange method of Y type molecular sieve |
| CN101745418B (en) * | 2008-11-28 | 2012-10-10 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
| CN102806096B (en) * | 2011-05-30 | 2014-12-31 | 中国石油化工股份有限公司 | Rare earth-containing Y-type molecular sieve cracking catalyst and preparation method thereof |
| JP5904922B2 (en) * | 2012-10-10 | 2016-04-20 | コスモ石油株式会社 | Hydrocarbon oil catalytic cracking catalyst and hydrocarbon oil catalytic cracking method |
| CN110193376B (en) * | 2018-02-26 | 2021-09-07 | 中国石油化工股份有限公司 | A kind of petroleum hydrocarbon catalytic cracking catalyst |
| CN110193377B (en) * | 2018-02-26 | 2021-09-07 | 中国石油化工股份有限公司 | A kind of petroleum hydrocarbon catalytic cracking catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065844A (en) * | 1991-04-18 | 1992-11-04 | 中国石油化工总公司石油化工科学研究院 | The preparation method of superstable Y type zeolite containing less rare-earth elements |
| CN1266882A (en) * | 1999-03-11 | 2000-09-20 | 中国石油化工集团公司 | Catalyst of cracking petroleum |
| US6528447B1 (en) * | 1999-03-19 | 2003-03-04 | Indian Oil Corporation Limited | Process for the preparation of a catalyst composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065844A (en) * | 1991-04-18 | 1992-11-04 | 中国石油化工总公司石油化工科学研究院 | The preparation method of superstable Y type zeolite containing less rare-earth elements |
| CN1266882A (en) * | 1999-03-11 | 2000-09-20 | 中国石油化工集团公司 | Catalyst of cracking petroleum |
| US6528447B1 (en) * | 1999-03-19 | 2003-03-04 | Indian Oil Corporation Limited | Process for the preparation of a catalyst composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11691132B2 (en) | 2018-08-17 | 2023-07-04 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof |
| TWI816857B (en) * | 2018-08-17 | 2023-10-01 | 大陸商中國石油化工科技開發有限公司 | Modified Y-type molecular sieve, catalytic cracking catalyst containing it, and preparation and use thereof |
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