CN1597850A - Catalytic cracking catalyst for reducing sulfur content of gasoline and preparation method thereof - Google Patents
Catalytic cracking catalyst for reducing sulfur content of gasoline and preparation method thereof Download PDFInfo
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- CN1597850A CN1597850A CN 03156915 CN03156915A CN1597850A CN 1597850 A CN1597850 A CN 1597850A CN 03156915 CN03156915 CN 03156915 CN 03156915 A CN03156915 A CN 03156915A CN 1597850 A CN1597850 A CN 1597850A
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- catalyzer
- microballoon
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- kaolin
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000003502 gasoline Substances 0.000 title claims abstract description 38
- 239000011593 sulfur Substances 0.000 title claims abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 28
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010457 zeolite Substances 0.000 claims abstract description 26
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- -1 rare-earth ions Chemical class 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000009466 transformation Effects 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910001723 mesolite Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 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
- 230000008859 change Effects 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 12
- 239000002808 molecular sieve Substances 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000005864 Sulphur Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011806 microball Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000021463 dry cake Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
A catalytic cracking catalyst for reducing sulfur content in gasoline is prepared through in-situ crystallizing kaolin to synthesize gamma-type molecular sieve, and exchanging to reduce sodium or/and rare-earth ions, and features that the weight percentage of sodium oxide contained in catalyst is less than 0.75%, the Si/Al ratio of zeolite is more than 4.5, and one or more of slightly acidic metal elements (Cu, Zn, Fe, Al, Ni, Zr, Sn, Ga, Ti and V) are added in it, and its weight percentage content is 0.1-10%. The catalyst has good zeolite dispersion and excellent hydrothermal stability, not only has good catalytic cracking performance, but also has an excellent function of reducing the sulfur content of gasoline. The catalyst can be used by being blended with a conventional FCC catalyst, and can also be independently applied to the catalytic cracking process.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst and preparation method thereof with reduction content of sulfur in gasoline function, more specifically, be a kind of be that feedstock production contains having of in-situ crystallization molecular sieve and reduces catalytic cracking catalyst of content of sulfur in gasoline and preparation method thereof with kaolin, this catalyzer can mix use with certain proportion with common FCC catalyzer, also can be used in the catalytic cracking process separately.
Background technology
Along with the environmental regulation increasingly stringent, various countries have formulated new gasoline standard in succession, especially wherein sulphur, olefin(e) centent are limited.Catalytic cracking is as one of main means of refining of petroleum, and FCC gasoline accounts for more than 80% of gasoline product total amount, and therefore, the sulphur content that reduces catalytically cracked gasoline is to reduce the key of content of sulfur in gasoline.Though can exist and invest big, the more high unfavorable factor of process cost by the pre-treatment of raw material hydrogenation or to means desulfurization such as FCC gasoline hydrofinishings, in addition, gasoline hydrogenation can reduce octane value because alkene is saturated.Desulfurization in catalytic cracking process does not need additional processing can realize reducing the purpose of content of sulfur in gasoline, is a kind of very attractive means from economic angle.
The catalyst additive that reduces at present content of sulfur in gasoline is at US5 by Wormsbecher and Kim, 376,608 and US5,525,210 described methods obtain, and Lewis acid is carried on the activated alumina, use as catalyst adjuvant, the effect of certain reduction content of sulfur in gasoline is arranged, but the industrial result of use of this auxiliary agent and not obvious.Li Chunyi etc. have announced a kind of catalytic cracking catalyst that reduces content of sulfur in gasoline in CN1356374A, adopt pickling process and coprecipitation method, supported rare earth and the metal oxide that has than large specific surface and appropriate acid on acid zeolite, one or more oxide compounds as Cu, Zn, Fe, Zr, Ga or Ti have the effect that reduces the FCC content of sulfur in gasoline preferably; Application No. 09/144,607 has been narrated a kind of catalyzer that is used for catalytic cracking process, introduces the metal component of the above oxidation state of zeroth order of period 4 in the zeolite, and wherein preferred vanadium improves the ability of the reduction content of sulfur in gasoline of catalytic cracking catalyst.
Prior art is all in the sulphur content that has reduced catalytically cracked gasoline in varying degrees, but the common drawback that exists is, the prepared auxiliary agent or the poor stability of catalyzer, and inactivation easily in use, thus increased the consumption of catalyzer.
Patent CN1232862A adopts the synthetic Y zeolite of kaolin in-situ crystallization, and its catalytic cracking function is very good, but does not have the content of sulfur in gasoline of reduction function.
Summary of the invention
Purpose of the present invention just is to avoid the deficiency of above-mentioned technology, provides a kind of and existing method the different catalytic cracking catalysts with reduction content of sulfur in gasoline function, makes its existing catalytic cracking function, has the content of sulfur in gasoline function of reduction and good stability again.
In order to realize purpose of the present invention, this catalytic cracking catalyst is by adopting the synthetic Y zeolite of Gao Ling ± in-situ crystallization, and exchange and fall sodium or/and rare earth ion exchanged is handled and obtained, the weight percent of the contained sodium oxide of catalyzer is less than 0.75%, the zeolite silica alumina ratio is more than 4.5, and simultaneously the operating weight degree is that 0.1～10% the scheme that metallic element modified catalyst that Cu, Zn, Fe, Al, Ni, Zr, Sn, Ga, Ti and V have appropriate acid combines that is selected from realizes.
More particularly, be kaolin to be added spray shaping is a microballoon after the water slurryization, the atomized microball roasting becomes the roasting microballoon.With mixing such as water glass, directed agents, roasting microballoons, system is the crystallization regular hour at a certain temperature, makes that in-situ crystallization grows zeolite (in detail referring to CN1232862A) in the microballoon.Contain in the microsphere of zeolite above-mentioned that to introduce weight percent content be that 0.1～10% metallic element with appropriate acid carries out modification, and with microballoon exchange fall sodium or and processing such as rare earth ion exchanged, the weight percent that makes the contained sodium oxide of catalyzer is less than 0.75%, the zeolite silica alumina ratio is more than 4.5, is catalyzer of the present invention.(following per-cent all is weight percentage except that specifying).
The metallic element of appropriate acid of the present invention, close with having of introducing among CN1356374A, the CN1261618A etc. than the metallic element of large specific surface and appropriate acid, can be the element that one or more are selected from Cu, Zn, Fe, Al, Ni, Zr, Sn, Ga, Ti and V, subacidity metallic element compound can be from its vitriol, nitrate, carbonate, acetate, muriate, and its add-on is preferably 0.1～2%.
Kaolin of the present invention is selected from dehydrated kaolin, the dehydrated kaolin of spinel type, sodium aluminum fluoride, the hydrous kaolin of metakaolin type.
The rare earth oxide weight percent content is 0～10% in the catalyzer of the present invention, and preferably the rare earth oxide weight percent content is 4～6%.
Catalyzer mesolite weight percent content of the present invention is preferably 15～60%, and particularly the zeolite weight percent content is 30～45%, more can make catalyzer of the present invention show excellent performance.
The present invention also recommends a kind of method for preparing catalyzer of the present invention:
(a) kaolin being added water, to make solid content be 15～60% slurries, adds the spray-dried kaolin microsphere parent that makes of paucidisperse agent;
(b) microballoon that makes at 700～1100 ℃ of calcination stepses (a) makes microballoon change into based on spinel and with the roasting microballoon of mullite on a small quantity through the heat release phase transformation;
(c) microballoon that step (b) is made mixes with the solution that comprises water glass, sodium hydroxide, directed agents, obtains the slurries of alkalescence, 60～120 ℃ of hydrothermal crystallizings 12～120 hours, removes by filter mother liquor, obtains containing the microballoon of y-type zeolite;
(d) microballoon that step (c) is made carries out ion-exchange and roasting, reduces its sodium content, makes its sodium oxide content be lower than 0.75%, perhaps can also carry out rare earth ion exchanged simultaneously.
(e) in above-mentioned (a)～(d) arbitrary steps or in the microballoon that makes of step (d), introduce subacidity metallic element compound with regulating catalyst acidity.
Dispersion agent of the present invention can be the dispersion agent of using always, and as being water glass, sodium hydroxide, trisodium phosphate, Sodium hexametaphosphate 99 etc., its add-on is 1～10% of a kaolin quality;
Select best condition as follows in the described alkaline slurry of step of the present invention (c): liquid phase SiO
2/ roasting microballoon=0.4～4.0; It consists of described directed agents: (10～18) SiO
2: (0.5～1.8) Al
2O
3: (12～18) Na
2O: (100～600) H
2O (mol ratio, as follows), naoh concentration are 7～50% (in detail referring to CN1232862A);
In the step of the present invention (d), the ion-exchange of microballoon and roasting can be carried out repeatedly repeatedly, do not limited its form among the present invention especially, as being " friendship, two friendships, three friendships, a roasting, four are handed over " among the CN1334314, " one hand over, two hand over, a roasting, three is handed over, two roastings " that also can be among the CN1232862 to be adopted, " one hand over, two hand over, a roasting, three is handed over, two roastings, four hand over " that can also be among the CN1334318 to be adopted etc., but finally to make its sodium oxide content be lower than 0.75%.The condition of ion-exchange is generally: ammonium salt/crystallization microballoon (quality, as follows)=0.2～0.5; Temperature is 80～100 ℃, and the pH value is 3.0～9, and maturing temperature is 400～650 ℃, and roasting time is 1～2 hour; Ammonium salt can adopt one or several to be selected from the compound of ammonium sulfate, ammonium chloride, ammonium nitrate, volatile salt, bicarbonate of ammonia.
The method that is adopted among the CN1334318 is used in special recommendation of the present invention, and is specific as follows:
(1) one hands over: in the ratio of ammonium sulfate/crystallization microballoon=0.2～0.5, adding crystallization microballoon and ammonium sulfate that step (c) makes successively, is 3.0～3.5 in the pH value, and temperature is 90～94 ℃ and exchanges 0.5～1 hour down, microballoon after the exchange after filtration, wash, refilter, one hand over material;
(2) two hand over: in the ratio of ammonium sulfate/crystallization microballoon=0.2～0. 5, hand over material with the ammonium sulfate exchange with one, pH value is 3.0～3.5, and temperature is 90～94 ℃, 0.5～1 hour time, the microballoon after the exchange after filtration, wash, refilter, two friendships are expected;
(3) one roastings: hand over material 500～700 ℃, roasting 0.5～3 hour with two, a roasting material;
(4) three hand over: a roasting material is to exchange 0.5～1 hour again under 3.0～4.5,90～94 ℃ of conditions with mixed chlorinated rare earth in the pH value, filters, washes, refilters the exchange product, gets three and hands over material; Wherein, rare earth/roasting material=0～10;
(5) two roastings: three filter cakes of handing over material 500～700 ℃ of roastings 0.5～3 hour, are got two roasting material;
(6) four hand over: the two roasting material condition of (1) exchange set by step replenish exchange once with ammonium sulfate, the exchange product after filtration, wash, refilter, drying, obtain the qualified microballoon of sodium oxide content.
Catalyzer of the present invention can mix use with certain proportion with common FCC catalyzer, also can be used in the catalytic cracking process separately.
Major advantage of the present invention and effect:
Because the method that adopts kaolin in-situ crystallization technology to combine with the metallic element modification of introducing appropriate acid, prepare the catalyzer that zeolite is scattered, hydrothermal stability is good, the function that had both had good reduction content of sulfur in gasoline has good catalytic cracking performance again.
Embodiment
Further the present invention is described below, but the present invention is not limited in these examples with embodiment.
(1) used analysis test method among the embodiment.
1. silica alumina ratio: X-ray diffraction is measured
2. little anti-sulphur performance evaluation of falling: catalyzer is pre-treatment 4h under 800 ℃, 100% water vapor condition in advance, mixes a certain amount of thiophene as reaction raw materials oil with the huge port solar oil, 472 ℃ of temperature of reaction, reaction times 120s, catalyzer loading amount 2.5g, air speed 16h
-1, reaction back product liquid sulphur content determination adopts WK-2C microcoulomb sulphur detector to analyze.
3. catalyst selectivity evaluation: catalyzer is pre-treatment 10h under 800 ℃, 100% water vapor condition in advance.Reaction raw materials oil is the isolated island wax oil of sulphur content 0.73%, 500 ℃ of temperature of reaction, air speed 12h
-1, agent-oil ratio 5.
(2) raw materials used specification among the embodiment
1. zinc nitrate, vanadylic sulfate, cupric nitrate, gallium chloride, tin chloride, iron protochloride, zirconium chloride, Tai-Ace S 150, titanium sulfate, nickelous nitrate, sodium hydroxide, trisodium phosphate, Sodium hexametaphosphate 99: be solid, chemical reagent.
2. kaolin: industrial goods.
3. ammonium chloride, ammonium sulfate, rare earth chloride: be industrial goods.
3. water glass: industrial goods contain 19.84% SiO
2, 6.98% Na
2O.
4. alkali lye: contain 14% NaOH.
Embodiment 1
10Kg (butt) protokaolin is added water, and to make solid content be 35% slurries, and add the 2.5Kg water glass as dispersion agent, spray shaping, the atomized microball of 8.5Kg.Atomized microball 940 ℃ of roastings in muffle furnace were got the roasting microballoon in 3 hours.Under whipped state, successively water glass 500ml, alkali lye 670ml, guiding agent for zeolite (are contained 11.65% SiO
2, 1.32% Al
2O
3, 12.89% Na
2O) 125ml, deionized water 200ml, roasting microballoon 1200g drop in the stainless steel reactor, are warmed up to 90 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain the crystallization product microballoon.Measure through X-ray diffraction, contain 23% NaY zeolite in the crystallization product microballoon, zeolite silica alumina ratio (mol ratio) is 4.6.The crystallization product microballoon adopts example 4 described ion-exchanges and high-temperature roasting treatment process among the CN1334318, and different is when three hand over, and three hand over rare earth/roasting material=5.Sodium oxide content is 0.50% in the microballoon that obtains after treatment, rare earth oxide content is 4.0%, then zinc nitrate 136g, gallium chloride 25g, tin chloride 20g are dissolved in the 260ml deionized water and form solution, with this microballoon of this solution impregnation 600g, microballoon behind the dipping is placed and is spent the night, at 120 ℃ of dry 4h, in 600 ℃ of roasting 1h, make catalyst A of the present invention more then.
Embodiment 2
All reaction raw materials are with embodiment 1, under agitation successively water glass 450ml, alkali lye 706ml, directed agents 160ml, deionized water 160ml, cupric nitrate 100g, iron protochloride 20g, zirconium chloride 12g, roasting microballoon 1100g are dropped in the stainless steel reactor, be warming up to 90 ℃ and thermostatic crystallization 20 hours.X-ray diffraction is measured crystallization product and is contained 19% NaY zeolite, and the zeolite silica alumina ratio is 5.2.The crystallization product microballoon adopts the method identical with embodiment 1 to carry out ion-exchange and high-temperature roasting is handled, and different is: three hand over rare earths/roastings to expect=3.Final microballoon sodium oxide content is 0.75%, and rare earth oxide content is 2.5%, makes catalyst B of the present invention.
Embodiment 3
10Kg (butt) protokaolin is added water, and to make solid content be 20% slurries, and add 0.2Kg sodium hydroxide, 0.2Kg trisodium phosphate, 0.1Kg Sodium hexametaphosphate 99 as dispersion agent, and spray shaping is a microballoon, the atomized microball of 8Kg.With an atomized microball part in muffle furnace in 950 ℃ of roastings 1 hour, roasting microballoon A, a part in 700 ℃ of roastings 1 hour, roasting microballoon B.Under whipped state, successively water glass 3000ml, alkali lye 900ml, guiding agent for zeolite 90ml, deionized water 200ml, each 500g of roasting microballoon A, B are dropped in stainless steel reactor, be warmed up to 90 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain the crystallization product microballoon.Measure through X-ray diffraction, contain 35% NaY zeolite in the crystallization product microballoon, zeolite silica alumina ratio (mol ratio) is 4.8.The crystallization product microballoon adopts the method identical with embodiment 1 to carry out ion-exchange and high-temperature roasting is handled, and different is: three hand over rare earths/roastings to expect=6.5.Sodium oxide content is 0.60% in the microballoon after the processing, rare earth oxide content is 5.2%, then this microballoon 600g, vanadylic sulfate 10g, Tai-Ace S 150 20g, deionized water 2000ml are dropped in the stainless steel reactor, 90 ℃ of constant temperature exchange 1 hour, make catalyzer C of the present invention.
Embodiment 4
Remove the crystallization product microballoon and fall sodium when handling exchanging, hand over and do not add in the exchange solution of processes the chlorination rare earth except three, other condition makes catalyzer D of the present invention with embodiment 3.
Embodiment 5
In embodiment 3, fall through exchange obtain that sodium oxide content is 0.60% after sodium and the calcination process, rare earth oxide content is 5.2% microballoon, this microballoon 600g, vanadylic sulfate 10g, nickelous nitrate 12g, titanium sulfate 20g, deionized water 2000ml are dropped in the stainless steel reactor, 90 ℃ of constant temperature exchange 1 hour, make catalyzer E of the present invention.
Comparative Examples 1
Except that not adopting zinc nitrate, gallium chloride, tin chloride dipping microballoon, other condition makes comparative catalyst's product F with embodiment 1.
Comparative Examples 2
Do not add in crystallization process cupric nitrate, iron protochloride, the zirconium chloride, other condition makes comparative catalyst's product G with embodiment 2.
Comparative Examples 3
Except that not adding vanadylic sulfate, Tai-Ace S 150, other condition makes comparative catalyst's product H with embodiment 3.
Comparative Examples 4
The LBO-12 catalyzer Industrial products that adopt PetroChina Lanzhou Petrochemical Company's catalyst plant to produce, this catalyzer adopts conventional semi-synthetic catalyst preparation process to be prepared from, and wherein the active ingredient zeolite content is 40%.This microballoon 600g, vanadylic sulfate 10g, Tai-Ace S 150 20g, deionized water 2000ml are dropped in the stainless steel reactor, and 90 ℃ of constant temperature exchange 1 hour, make comparative catalyst I.
Catalyzer F, G, H that catalyst A of the present invention, B, C, D, E and the Comparative Examples 1～3 that embodiment 1～5 is prepared prepares estimate at micro-reactor, the results are shown in table 1.Wt% all refers to weight percent in the table.
Wherein, in the table 1, liquid is received=(liquid weight/stock oil weight that stock oil is collected through the reaction postcooling) * 100%; R represents relative reduction amplitude and the absolute reduction amplitude of sulfur-bearing oil through the collected product liquid sulphur content in micro-reactor reaction back respectively with Rt:
R=(the stock oil sulphur content-collected product liquid sulphur content in reaction back)/stock oil sulphur content * 100%;
Rt=(the collected product liquid sulphur content * liquid in stock oil sulphur content-reaction back is received)/stock oil sulphur content * 100%.
The micro anti-evaluation result of the various catalyzer of table 1 (stock oil sulfur-bearing 1341 μ gml
-1)
| Project | Application Example gained catalyzer | Use Comparative Examples gained catalyzer | ||||||
| ??A | ??B | ??C | ??D | ??E | ??F | ??G | ??H | |
| Reaction back oil product sulfur-bearing, μ gml -1 | ??910 | ??924 | ??843 | ??824 | ??840 | ??1031 | ??1100 | ??986 |
| Liquid is received, wt% | ??87.4 | ??88.2 | ??85.5 | ??88.5 | ??86.2 | ??87.8 | ??89.2 | ??84.6 |
| ??R，％ | ??32.1 | ??31.1 | ??37.1 | ??38.6 | ??37.4 | ??23.1 | ??18.0 | ??26.5 |
| ??Rt，％ | ??40.7 | ??39.2 | ??46.2 | ??45.6 | ??46.0 | ??32.5 | ??26.8 | ??37.8 |
As seen from Table 1, compare with Comparative Examples gained catalyzer, introduce the element modified catalyzer of the present invention of Special Metal, further reduced the sulphur content of reaction back gained product liquid, illustrate that catalyzer of the present invention has the function of good reduction light-end products sulphur content.
With the catalyzer C of the present invention of embodiment 3 preparation and the catalyzer H of Comparative Examples 3 preparations, the catalyst I of Comparative Examples 4 preparations, on small fixed flowing bed-tion reacting device (catalyzer loading amount 180 grams), carry out cracking reaction performance evaluation, the product of reaction distributes and the content of sulfur in gasoline data are listed in the table 2.In the table 2, total liquid is received the weight percentage sum for reaction back liquefied gas, gasoline, diesel oil, the light weight percentage sum of receiving to reaction back gasoline, diesel oil.Transformation efficiency refers to stock oil through after reacting, the summation of the weight percentage of dry gas, liquefied gas, gasoline, coke in the product distributional analysis.Dry gas yield/transformation efficiency refers to the ratio of dry gas yield and transformation efficiency, and other gasoline, coking yield/transformation efficiency duplicate.
The cracking reaction evaluation result of table 2 catalyzer
| Catalyzer | Application Example 3 gained catalyzer C | Use Comparative Examples 3 gained catalyzer H | Use Comparative Examples 4 gained catalyst I |
| Reacted material balance, wt% | |||
| Dry gas | ??3.04 | ??3.11 | ??2.61 |
| Liquefied gas | ??14.92 | ??18.34 | ??15.35 |
| Gasoline | ??49.55 | ??52.00 | ??43.41 |
| Diesel oil | ??19.14 | ??15.21 | ??22.61 |
| Heavy oil | ??8.23 | ??5.48 | ??11.80 |
| Coke | ??4.64 | ??5.41 | ??3.77 |
| Amount to | ??99.52 | ??99.52 | ??99.55 |
| Transformation efficiency, wt% | ??72.15 | ??78.86 | ??65.14 |
| Light receipts, wt% | ??68.69 | ??67.21 | ??66.02 |
| Total liquid is received wt% | ??83.61 | ??85.55 | ??81.37 |
| Product selectivity | |||
| Dry gas yield/transformation efficiency | ??0.0421 | ??0.0394 | ??0.0401 |
| Yield of gasoline/transformation efficiency | ??0.687 | ??0.659 | ??0.666 |
| Coking yield/transformation efficiency | ??0.0643 | ??0.0686 | ??0.0579 |
| Content of sulfur in gasoline, μ gml -1 | ??442 | ??694 | ??470 |
Found out by table 2 data, compare with comparative catalyst H that catalyzer C light-end products selectivity of the present invention is good, coke does not increase, and content of sulfur in gasoline reduces about 36%, has shown good reduction content of sulfur in gasoline function.Though comparative catalyst I reduces the effect of content of sulfur in gasoline in catalytic cracking process also better, but it is still low that catalyzer C of the present invention and Comparative Examples 4 gained catalyst I are compared content of sulfur in gasoline, be lower than under the situation of comparative catalyst I at catalyzer C zeolite content of the present invention, the cracking reaction transformation efficiency illustrates that but apparently higher than contrast medium the stability of catalyzer of the present invention obviously is better than reducing the similar catalyst of content of sulfur in gasoline.
Claims (14)
1. catalytic cracking catalyst that reduces content of sulfur in gasoline, be that kaolin in-situ crystallization synthesizes Y zeolite after adopting roasting, and exchange fall sodium or and rare earth ion exchanged handle and obtain, the weight percent that it is characterized in that the contained sodium oxide of catalyzer is less than 0.75%, the zeolite silica alumina ratio is more than 4.5, and contain one or more and be selected from Cu, Zn, Fe, Al, Ni, Zr, Sn, Ga, Ti and V subacidity metallic element, its weight percent content is 0.1～10%.
2. catalyzer according to claim 1 is characterized in that kaolin can be one or more of dehydrated kaolin, sodium aluminum fluoride, hydrous kaolin of the dehydrated kaolin that is selected from the metakaolin type, spinel type.
3. catalyzer according to claim 1 is characterized in that the subacidity metallic element that added, and its weight percent content is 0.1～2%.
4. catalyzer according to claim 1 is characterized in that catalyzer mesolite weight percent content is 15～60%.
5. catalyzer according to claim 1 is characterized in that catalyzer mesolite weight percent content is 30～45%.
6. catalyzer according to claim 1 is characterized in that the rare earth oxide weight percent content is 0～10% in the catalyzer.
7. catalyzer according to claim 1 is characterized in that the rare earth oxide weight percent content is 4～6% in the catalyzer.
8. described Preparation of catalysts method of claim 1, by the method preparation of following step:
(a) kaolin being added water, to make solid content be 15～60% slurries, adds dispersion agent, and spray-dried aqueous slurry makes microballoon;
(b) microballoon that makes at 700～1100 ℃ of calcination stepses (a) makes microballoon change into based on spinel and with the roasting microballoon of mullite on a small quantity through the heat release phase transformation;
(c) microballoon that step (b) is made mixes with the solution that comprises water glass, sodium hydroxide, directed agents, obtains the slurries of alkalescence, 60～120 ℃ of hydrothermal crystallizings 12～120 hours, removes by filter mother liquor, obtains containing the microballoon parent of y-type zeolite;
(d) the microballoon parent that step (c) is made carries out ion-exchange and roasting, reduces its sodium content, makes its sodium oxide content be lower than 0.75%.
(e) in above-mentioned (a)～(d) arbitrary steps or in the microballoon that makes of step (d), introduce subacidity metallic element compound.
9. Preparation of catalysts method according to claim 8 is characterized in that carrying out rare earth ion exchanged in (d) step.
10. Preparation of catalysts method according to claim 8 is characterized in that in the described alkaline slurry of step (c) liquid phase SiO
2With the weight ratio of roasting microballoon be 0.4～4.0.
11. Preparation of catalysts method according to claim 8 is characterized in that the weight percent concentration of sodium hydroxide is 7～50% in the described alkaline slurry of step (c).
12. Preparation of catalysts method according to claim 8 is characterized in that in the step (c), its constitutive molar ratio of directed agents is: (10～18) SiO
2: (0.5～1.8) Al
2O
3: (12～18) Na
2O: (100～600) H
2O.
13. Preparation of catalysts method according to claim 8 is characterized in that described subacidity metallic element compound can be from its vitriol, nitrate, carbonate, acetate, muriate.
14. Preparation of catalysts method according to claim 8 is characterized in that described dispersion agent can be selected from one or more of water glass, sodium hydroxide, trisodium phosphate, Sodium hexametaphosphate 99, its add-on is 1～10% of a kaolin weight.
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