CN100389176C - A cracking aid for increasing propylene production - Google Patents
A cracking aid for increasing propylene production Download PDFInfo
- Publication number
- CN100389176C CN100389176C CNB2004101028157A CN200410102815A CN100389176C CN 100389176 C CN100389176 C CN 100389176C CN B2004101028157 A CNB2004101028157 A CN B2004101028157A CN 200410102815 A CN200410102815 A CN 200410102815A CN 100389176 C CN100389176 C CN 100389176C
- Authority
- CN
- China
- Prior art keywords
- heavy
- additive
- kilograms
- weight
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000005336 cracking Methods 0.000 title claims abstract description 49
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 24
- 230000001965 increasing effect Effects 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 103
- 230000000996 additive effect Effects 0.000 claims abstract description 67
- 239000011777 magnesium Substances 0.000 claims abstract description 40
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 39
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004927 clay Substances 0.000 claims abstract description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 49
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 45
- 239000005995 Aluminium silicate Substances 0.000 claims description 42
- 235000012211 aluminium silicate Nutrition 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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 6
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 38
- 238000004523 catalytic cracking Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 76
- 239000010457 zeolite Substances 0.000 description 66
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 65
- 229910021536 Zeolite Inorganic materials 0.000 description 64
- 239000002002 slurry Substances 0.000 description 40
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 36
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 32
- 238000010009 beating Methods 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 25
- 239000004411 aluminium Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000001035 drying Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 238000005507 spraying Methods 0.000 description 19
- 229910001629 magnesium chloride Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011592 zinc chloride Substances 0.000 description 16
- 235000005074 zinc chloride Nutrition 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 150000002681 magnesium compounds Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 101000643890 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 5 Proteins 0.000 description 3
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 101000643895 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 6 Proteins 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 102100021015 Ubiquitin carboxyl-terminal hydrolase 6 Human genes 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
本发明公开了一种增产丙烯的裂化助剂，其特征在于该助剂按干基计，由10～65重%的改性ZSM-5分子筛、0～60重%的粘土、15～70重%的无机氧化物粘结剂、0.5～10重%的镁添加剂和0.5～15重%的锌添加剂组成，其中所说的改性ZSM-5分子筛经磷和选自Fe、Co或Ni之一的金属改性，其无水化学表达式，以氧化物计为(0～0.3)Na2O·(0.5～5)Al2O3·(1.3～10)P2O5·(0.7～15)MxOy·(70～97)SiO2，x表示M的原子数，y表示满足M氧化态所需的一个数，所说的粘结剂、镁添加剂和锌添加剂均是以氧化物计。该助剂应用于石油烃的催化裂化过程中，在增加催化裂化液化气产率和提高催化裂化汽油辛烷值的同时，可较大幅度地提高液化气中的丙烯浓度。The invention discloses a cracking auxiliary agent for increasing the production of propylene, which is characterized in that the auxiliary agent consists of 10-65% by weight of modified ZSM-5 molecular sieve, 0-60% by weight of clay, 15-70% by weight of % inorganic oxide binder, 0.5-10 wt% magnesium additive and 0.5-15 wt% zinc additive, wherein the modified ZSM-5 molecular sieve is treated with phosphorus and selected from one of Fe, Co or Ni The metal modification, its anhydrous chemical expression, in terms of oxides, is (0~0.3)Na 2 O·(0.5~5)Al 2 O 3 ·(1.3~10)P 2 O 5 ·(0.7~15 )M x O y ·(70～97)SiO 2 , x represents the number of atoms of M, and y represents a number required to satisfy the oxidation state of M. The binder, magnesium additive and zinc additive are all oxides count. The additive is applied in the catalytic cracking process of petroleum hydrocarbons. While increasing the yield of catalytic cracked liquefied gas and the octane number of catalytic cracked gasoline, it can greatly increase the concentration of propylene in the liquefied gas.
Description
Technical field
The invention relates to a kind of cracking additive, further say so about a kind of cracking additive of propylene enhancing of the ZSM-5 of containing molecular sieve.
Background technology
Propylene is important Organic Chemicals, and along with increasing rapidly of derivative demands such as polypropylene, the whole world is also all increasing year by year to the demand of propylene.Fluid catalytic cracking is to produce one of important production technique of light olefin and propylene.For most of catalytic cracking unit, for increasing light olefin yield and propylene, it is the otherwise effective technique approach that employing contains catalyzer or auxiliary agent with MFI structural zeolite.
USP3,758,403 early are disclosed in the method for adding the ZSM-5 zeolite in the catalytic cracking catalyst can improve the octane value of gasoline and increase C
3～C
4The productive rate of alkene.For example, add in containing the conventional catalyst of 10%REY behind 1.5,2.5,5 to 10% ZSM-5 zeolite, gasoline octane rating improves, the gain in yield of low-carbon alkene; Use also has same effect when containing the auxiliary agent of ZSM-5 zeolite.
USP 5,318, proposed the hydrocarbon conversion process process of the catalyzer formed less than 30 the zeolite with MFI structure based on a kind of large pore zeolite and silica alumina ratio in 696.This technology is produced stop bracket gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.
USP 5,997, disclose a large amount of methods of using the shape slective cracking auxiliary agents in the heavy feed stock catalytic cracking process in 728.Said auxiliary agent is made up of the ZSM-5 zeolite that adds 12～40% in the [amorphous, and system's reserve at least 10% makes the ratio of ZSM-5 in catalyzer surpass 3%.This method can additionally not increase aromatic production and loss gasoline yield when increasing substantially low-carbon alkene.
After the ZSM-5 zeolite carried out modification with P contained compound, its cracking activity stability can improve, and reduced the consumption of zeolite.
The zeolite that discloses a kind of phosphorous and rare earth among the CN 1049406C and had the MFI structure, its anhydrous chemical constitution is aRE
2O
3BNa
2OAl
2O
3CP
2O
5DSiO
2, a=0.01～0.25 wherein, b=0.005～0.02, c=0.2～1.0, d=35～120.This zeolite has excellent hydrothermal activity stability and good selectivity of light olefin when being used for the hydro carbons pyrolytic conversion.
Disclose a kind of catalyst for cracking that is used to produce low-carbon alkene among the CN 1034223C, formed by the clay of 0～70% (is benchmark with the catalyst weight), 5～99% inorganic oxide and 1～50% zeolite.Zeolite wherein is the mixture of the five-ring supersiliceous zeolite of the REY of 0～25 heavy % or the phosphorous and rare earth that type-Y high silicon zeolite and 75～100 weighs %.It is higher hydro-thermal activity stability, transformation efficiency and the C of catalyzer of active ingredient with the ZSM-5 zeolite that this catalyzer has
2 =～C
4 =Productive rate.
USP5 discloses the preparation method with the ZSM-5 zeolite catalyst of phosphorus modification in 110,776.Said phosphorus modifying process is that zeolite is dispersed in the P contained compound aqueous solution of pH value 2～6, then with matrix making beating, spray drying forming.The gained catalyzer does not increase dry gas and coke yield when improving gasoline octane rating.
USP6 discloses a kind of cracking catalyst of phosphorous modified ZSM-5 zeolite in 566,293.The preparation of said phosphorous modified ZSM-5 is that zeolite is dispersed in the P contained compound aqueous solution of pH value more than 4.5, and the phosphorus that makes zeolite-loaded at least 10 heavy % is (with P
2O
5Meter), pull an oar spray drying forming with matrix and other zeolite component then.The gained catalyzer has higher productivity of low carbon olefin hydrocarbon.
USP5 discloses a kind of ZSM-5 zeolite with the phosphorus modification in 171,921.This zeolite has 20～60 silica alumina ratio, with P contained compound dipping after after 500～700 ℃ of steam-treated, be used for C
3～C
20Hydrocarbon changes into C
2～C
5During the reaction of alkene, the ZSM-5 that handles without phosphorus has higher activity relatively.
USP6 discloses a kind of method that improves aperture and mesopore zeolite catalytic activity in 080,303.This method is to handle aperture and mesopore zeolite with phosphorus compound, then the zeolite and the AlPO that will handle through phosphorus
4The gel combination.This method can be improved the activity and the hydrothermal stability of aperture and mesopore zeolite.
USP5 discloses the hydrocarbon conversion process process of the catalyzer of forming based on a kind of large pore zeolite and phosphorated MFI structure mesopore zeolite in 472,594.This technology is produced stop bracket gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly C
4/ C
5
Also report and in matrix, introduce phosphorus compound the phosphorus modification except the ZSM-5 zeolite is carried out, can improve catalyzer or auxiliary agent selectivity low-carbon alkene.
A kind of catalytic cracking process process that increases productivity of propylene is disclosed among USP 2002/0003103 A1.This technological process is carried out the cracking reaction near small part gasoline product enters second riser tube again, in the catalyst composition that is adopted except containing macropore USY zeolite, the mineral binder bond component that also contains mesopore zeolites such as ZSM-5 and have cracking performance.Phosphorous in the mineral binder bond component wherein, its P/Al ratio is 0.1～10.This technological process is increased low carbon olefine output significantly, particularly increases productivity of propylene.
The catalyzer of a kind of high zeolite content, high abrasion resistance strength is disclosed among USP 2002/0049133 A1.This catalyzer contains the ZSM-5 zeolite of 30～85 heavy %, and the phosphorus of 6～24 heavy % is (with P
2O
5Count), and the Al that is lower than 10 heavy %
2O
3With other components such as clay of surplus, phosphorus wherein is present in the matrix.This catalyzer is used for catalytic cracking process, can increase light olefin, especially productivity of propylene.
Zeolite has following relevant report with metal-modified method and application thereof.For example USP 5,236, disclose the catalyzer that contains MFI or MEL structural zeolite in 880.Wherein used zeolite is through VIII family metal, preferably with the Ni modification, and after this zeolite was introduced Ni, heat or hydrothermal treatment consists under the controlled temperature of experience harshness made VIII family metal and aluminium at surface enrichment.Said catalyzer is used for can improving gasoline octane rating when alkane transforms, and increases C
3～C
4The productive rate of alkene.
A kind of catalyst for cracking that contains supersiliceous zeolite is disclosed among the CN 1057408A, has higher catalytic pyrolysis activity, wherein said supersiliceous zeolite is ZSM-5, β zeolite or the mordenite that contains 0.01～3.0 heavy % phosphorus, 0.01～1.0 heavy % iron or 0.01～10 heavy % aluminium, be that silica alumina ratio is heated to 350～820 ℃ greater than 15 Hydrogen or potassium type ZSM-5 zeolite, β zeolite or mordenite, with 0.1～10 hour
-1Volume space velocity obtain after feeding the halide solution of halide solution, iron of aluminium or saline solution of ammonium phosphate.
Disclose a kind of MFI structural zeolite of phosphorous and transition metal among the CN 1465527A, the anhydrous chemical expression of this zeolite is counted (0～0.3) Na with the quality of oxide compound
2O (0.5～5) Al
2O
3(1.3～10) P
2O
5(0.7～15) M
2O
3(70～97) SiO
2, wherein, M is selected from a kind of among transition-metal Fe, Co and the Ni.When this zeolite is applied to the catalytic cracking process of petroleum hydrocarbon, can improve C
2～C
4The productive rate of alkene and selectivity have higher liquefied gas yield.
At present, for the overwhelming majority's catalytic cracking unit, under the prerequisite of identical liquefied gas yield, the density of propylene that improves in the liquefied gas is the important channel of improving the catalytic cracking unit economic benefit.Disclosed zeolitic material of prior art and catalyzer are used for catalytic cracking process, though can increase the productive rate of low-carbon alkene effectively, improve the octane value of catalytically cracked gasoline product, but the selectivity for propylene in the catalytic cracking reaction process is not very high, thereby the amplitude that improves density of propylene in the liquefied gas is limited.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of cracking additive of propylene enhancing, this auxiliary agent is applied in the catalytic cracking process, can not only increase the catalytic cracking liquefied gas yield effectively, improve the octane value of catalytically cracked gasoline, can also improve the density of propylene in the catalytic cracking liquefied gas simultaneously greatly.
The inventor finds, with disclosed phosphorous and modified zsm-5 zeolite transition metal among the CN 1465527A is active component, further introduce an amount of magnesium additive and zinc additive, prepared cracking additive is applied to can reach purpose of the present invention in the catalytic cracking process of petroleum hydrocarbon.
Therefore, the cracking additive of propylene enhancing provided by the present invention, it is characterized in that this auxiliary agent is by butt, form by the modified zsm-5 zeolite of 10～65 heavy %, the clay of 0～60 heavy %, the inorganic oxide binder of 15～70 heavy %, the magnesium additive of 0.5～10 heavy % and the zinc additive of 0.5～15 heavy %, wherein said modified zsm-5 zeolite is the ZSM-5 molecular sieve through phosphorus and is selected from the metal-modified of one of Fe, Co or Ni and obtains, its anhydrous chemical expression is counted (0～0.3) Na with oxide compound
2O (0.5～5) Al
2O
3(1.3～10) P
2O
5(0.7～15) M
xO
y(70～97) SiO
2, x represents the atomicity of M, and y represents to satisfy the required number of M oxidation state, and said binding agent, magnesium additive and zinc additive all are in oxide compound.
Cracking additive provided by the present invention is by butt, and preferred group becomes the modified zsm-5 zeolite of 20～50 heavy %, the clay of 20～40 heavy %, the inorganic oxide binder of 25～50 heavy %, the magnesium additive of 1～5 heavy % and the zinc additive of 2～10 heavy %.
Under the preferable case, described modified zsm-5 zeolite is through phosphorus and Fe modification, and its anhydrous chemical expression is counted (0～0.2) Na with oxide compound
2O (0.9～3.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2
Cracking additive provided by the present invention, wherein said clay is conventionally known to one of skill in the art, the present invention has no particular limits it, can be selected from one or more the mixture that comprises in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, the tired clay material that takes off stone, diatomite, halloysite, saponite, boron-moisten soil, hydrotalcite.Wherein preferably kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired one or more the mixture that takes off in the stone.
Cracking additive provided by the present invention, wherein said inorganic oxide binder are selected from as in the inorganic oxide of auxiliary agent matrix and binder component one or more, and they are conventionally known to one of skill in the art, and the present invention has no particular limits it.Described inorganic oxide binder can be one or more the mixture that comprises pseudo-boehmite, aluminium colloidal sol, silicon-aluminum sol, water glass, wherein the mixture of pseudo-boehmite and aluminium colloidal sol preferably.
Cracking additive provided by the present invention can be by zeolite, clay, inorganic oxide binder, and magnesium additive and zinc additive adopt any method in the existing cracking catalyst technology of preparing that comprises spray drying forming to prepare, and the present invention has no particular limits it.
Described magnesium additive and zinc additive exist with the form of magnesium compound (as the oxide compound of magnesium, aluminate, silicate, aluminosilicate etc.) and zn cpds (as the oxide compound of zinc, aluminate, silicate, aluminosilicate etc.).
Described magnesium compound is selected from the various mineral compound of magnesium and in the organic compound one or more, can be soluble in water, also can be to be insoluble in water or water-fast.The example of magnesium compound comprises oxide compound, muriate, nitrate, vitriol, carbonate, acid carbonate, subcarbonate and the magniferous organic compound etc. of magnesium, and wherein preferred magnesium compound is selected from one or more in muriate, vitriol and the nitrate.
Described zn cpds is selected from the various mineral compound of zinc and in the organic compound one or more, can be soluble in water, also can be to be insoluble in water or water-fast.The example of zn cpds comprises oxide compound, muriate, nitrate, vitriol, carbonate, acid carbonate, subcarbonate and the zinciferous organic compound etc. of zinc, and wherein preferred zn cpds is selected from one or more in muriate, vitriol and the nitrate.
Said magnesium compound and/or zn cpds can add in slurries before the spray drying forming of auxiliary agent, also can the process by dipping or chemisorption introduce after the auxiliary agent spray drying forming.Thereby, described magnesium additive and zinc additive may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of zeolite, the surface of zeolite, and may reside in the substrate material, can also be present in simultaneously in the surface and substrate material thereof of inside, duct, zeolite of zeolite.
When described magnesium additive and/or zinc additive are when introducing in the auxiliary agent after the spray drying forming, the preparation method comprises floods the aqueous solution of auxiliary agent with magnesium-containing compound and/or zinc compound or the chemisorption processing, carry out the process of solid-liquid separation (if necessary), drying and roasting then, wherein the exsiccant temperature is a room temperature to 400 ℃, preferred 100-300 ℃, the temperature of roasting is 400-700 ℃, be preferably 450-650 ℃, roasting time is 0.5-100 hour, is preferably 0.5-10 hour.
When cracking additive provided by the invention is used for catalytic cracking process, can in catalyst cracker, add separately, also can mix the back with cracking catalyst and use.Generally speaking, cracking additive provided by the invention accounts for 1～25 heavy %, preferred 3～15 heavy % of the FCC catalyzer and the gross weight of the mixture that the invention provides cracking additive.
Cracking additive provided by the invention can be used for the processing of various hydrocarbon ils, described hydrocarbon ils is selected from various petroleum fractionss, as crude oil, long residuum, vacuum residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/in heavily de-oiling, wax tailings and the gelatin liquefaction product one or more.Described hydrocarbon ils can contain beavy metal impurity such as nickel, vanadium and sulphur, nitrogen impurity, can be as the content of sulphur up to 3.0 heavy %, and the content of nitrogen can be up to 2.0 heavy %, and the content of metallic impurity such as vanadium, nickel is up to 3000ppm.
Cracking additive provided by the invention is used for catalytic cracking process, and the cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, this cracking hydrocarbon oil condition comprises that temperature of reaction is 400-600 ℃, is preferably 450-550 ℃, and weight hourly space velocity is 10-120 hour
-1, be preferably 10-80 hour
-1, the agent weight of oil is than being 1-20, being preferably 3-15.
Cracking additive provided by the invention can be used for existing various catalyst cracker, as carrying out in fixed-bed reactor, fluidized-bed reactor, riser reactor, multi-reaction-area reactor etc.
The cracking additive of propylene enhancing provided by the present invention, adopting phosphorus and metal-modified ZSM-5 molecular sieve is active component, and introduced an amount of magnesium, zinc additive, and can obviously improve the selectivity of catalytic cracking reaction process for propylene, improve the density of propylene in the liquefied gas greatly.
Embodiment
The following examples will be further described the present invention, but content not thereby limiting the invention.
Among the embodiment, A
1～A
8Eight modified zsm-5 zeolite samples are by the disclosed method preparation of CN1465527A, and its anhydrous chemical expression is use the x-ray fluorescence spectrometry molecular sieve elementary composition, obtains through conversion again.
Sample A
1: 0.04Na
2O3.57Al
2O
34.0P
2O
52.4Fe
2O
390.49SiO
2
Sample A
2: 0.1Na
2O5.0Al
2O
32.0P
2O
50.9Fe
2O
392SiO
2
Sample A
3: 0.1Na
2O5.3Al
2O
31.5P
2O
51.1Fe
2O
392SiO
2
Sample A
4: 0.03Na
2O2.2Al
2O
34.9P
2O
52.1Fe
2O
390.8SiO
2
Sample A
5: 0.1Na
2O0.94Al
2O
35.1P
2O
510.1Fe
2O
384SiO
2
Sample A
6: 0.03Na
2O5.1Al
2O
34.8P
2O
53.6Co
2O
386.5SiO
2
Sample A
7: 0.1Na
2O4.6Al
2O
36.9P
2O
56.4Ni
2O
382SiO
2
Sample A
8: 0.1Na
2O5.2Al
2O
34.5P
2O
52.0Ni
2O
388.2SiO
2
Among the embodiment and in the Comparative Examples, the ZRP-5 zeolite is the Industrial products of the conventional MFI structural zeolite of Qilu Petrochemical catalyst plant production, wherein P
2O
52.5 heavy %, degree of crystallinity 85 heavy %, silica alumina ratio 50; Pseudo-boehmite is Shandong Aluminum Plant's manufacture product, solid content 60 heavy %; The Industrial products that aluminium colloidal sol is produced for the Qilu Petrochemical catalyst plant, Al
2O
3Content is 21.5 heavy %; Kaolin is the special-purpose kaolin of cracking catalyst that Suzhou kaolin company produces, solid content 78 heavy %; Magnesium chloride and zinc chloride are chemically pure reagent, are the Beijing Chemical Plant and produce.
The preparation process of embodiment 1～16 explanation cracking additive provided by the invention.
Embodiment 1
Get 1.84 kilograms of (butt) A
1, 1.58 kilograms of (butt) kaolin and 0.98 kilogram of (butt) pseudo-boehmite, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 36.8 heavy %A
1, 31.6 heavy % kaolin and 31.6 heavy %Al
2O
3Microballoon.
Get 1 kilogram of thus obtained microsphere product (butt), carry out saturated dipping, left standstill 12 hours, 120 ℃ down after the oven dry,, make and contain 35 heavy %A in 500 ℃ of following roastings 2 hours with 3 liters of mixed aqueous solutions that contain magnesium chloride and zinc chloride (wherein containing MgO 10 grams, ZnO 40 grams)
1, 30 heavy % kaolin, 30 heavy %Al
2O
3, and the auxiliary agent ZJ of 1 heavy % magnesium additive (in MgO) and 4 heavy % zinc additives (in ZnO)
1
Embodiment 2
Get 1.94 kilograms of (butt) A
1With 2.46 kilograms of (butt) pseudo-boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 38.89 heavy %A
1With 61.11 heavy %Al
2O
3Microballoon.
Get 1 kilogram of thus obtained microsphere product (butt), carry out saturated dipping, left standstill 12 hours, 120 ℃ down after the oven dry,, make and contain 35 heavy %A in 500 ℃ of following roastings 2 hours with 3 liters of mixed aqueous solutions that contain magnesium chloride and zinc chloride (wherein containing MgO 30 grams, ZnO 70 grams)
1, 55 heavy %Al
2O
3, and the auxiliary agent ZJ of 3 heavy % magnesium additives (in MgO) and 7 heavy % zinc additives (in ZnO)
2
Embodiment 3
Get 1.32 kilograms of (butt) A
1, 1.84 kilograms of (butt) kaolin, 0.98 kilogram of (butt) pseudo-boehmite and 2 liters of magnesium chloride brines (wherein containing MgO 263.2 grams), add 5.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 26.3 heavy %A
1, 36.8 heavy % kaolin, 31.6 heavy %Al
2O
3Microballoon with 5.26 heavy % magnesium additives (in MgO).
Get 1 kilogram of thus obtained microsphere product (butt), carry out saturated dipping, left standstill 12 hours, 120 ℃ down after the oven dry,, make and contain 25 heavy %A in 500 ℃ of following roastings 2 hours with 3 liters of solder(ing)acids (wherein contain ZnO 50 gram)
1, 35 heavy % kaolin, 30 heavy %Al
2O
3, and the auxiliary agent ZJ of 5 heavy % magnesium additives (in MgO) and 5 heavy % zinc additives (in ZnO)
3
Embodiment 4
Get 1.84 kilograms of (butt) A
1, 1.32 kilograms of (butt) kaolin, 0.98 kilogram of (butt) pseudo-boehmite and 2 liters of solder(ing)acids (wherein containing ZnO 263.2 grams), add 5.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 36.8 heavy %A
1, 26.3 heavy % kaolin, 31.6 heavy %Al
2O
3Microballoon with 5.26 heavy % zinc additives (in ZnO).
Get 1 kilogram of thus obtained microsphere product (butt), carry out saturated dipping, left standstill 12 hours, 120 ℃ down after the oven dry,, make and contain 35 heavy %A in 500 ℃ of following roastings 2 hours with 3 liters of magnesium chloride brines (wherein contain MgO 50 gram)
1, 25 heavy % kaolin, 30 heavy %Al
2O
3, and the auxiliary agent ZJ of 5 heavy % magnesium additives (in MgO) and 5 heavy % zinc additives (in ZnO)
4
Embodiment 5
Get 2.0 kilograms of (butt) A
1, 0.9 kilogram of (butt) kaolin, 3 liters of mixed aqueous solution (wherein containing MgO 100 grams, ZnO 500 grams) and 5.19 kg of water glass (production of Qilu Petrochemical catalyst plant, SiO that contain magnesium chloride and zinc chloride
2Content 28.9 heavy %, Na
2O content 8.9%), add 2 kilograms of decationized Y sieve water making beating 120 minutes, stir and add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture continues 45 fens kinds of making beating, and the slurries that obtain 500 ℃ of temperature ins, are carried out spraying drying under the condition that exhaust temperature is 180 ℃, obtains average particulate diameter and be 65 microns microballoon.With microballoon in 400 ℃ of following roastings 1 hour.
Get 1 kilogram of the microballoon (butt) after the above-mentioned roasting, add 10 liters of decationized Y sieve water and 100 gram ammonium chlorides, stir down and be warming up to 60 ℃, after washing 20 minutes under this temperature, the slurries vacuum filtration.By above identical method filter cake is relaundered once, under 120 ℃ of temperature, dry, make and contain 40 heavy %A
1, 18 heavy % kaolin, 30 heavy %SiO
2, and the auxiliary agent ZJ of 2 heavy % magnesium additives (in MgO) and 10 heavy % zinc additives (in ZnO)
5
Embodiment 6
Get 1.75 kilograms of (butt) A
1, 1.75 kilograms of (butt) kaolin and 0.85 kilogram of (butt) pseudo-boehmite, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 200 grams, ZnO 300 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 25 heavy % kaolin, 30 heavy %Al
2O
3, and the auxiliary agent ZJ of 4 heavy % magnesium additives (in MgO) and 6 heavy % zinc additives (in ZnO)
6
Embodiment 7
Get 1 kilogram of (butt) A
2, 2.15 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-boehmite, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 250 grams, ZnO 100 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 20 heavy %A
2, 43 heavy % kaolin, 30 heavy %Al
2O
3, and the auxiliary agent ZJ of 5 heavy % magnesium additives (in MgO) and 2 heavy % zinc additives (in ZnO)
7
Embodiment 8
Get 1.25 kilograms of (butt) A
3, 1 kilogram of (butt) kaolin and 1.3 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 250 grams, ZnO 600 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 25 heavy %A
3, 20 heavy % kaolin, 38 heavy %Al
2O
3, and the auxiliary agent ZJ of 5 heavy % magnesium additives (in MgO) and 12 heavy % zinc additives (in ZnO)
8
Embodiment 9
Get 2 kilograms of (butt) A
40.75 kilogram (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 100 grams, ZnO 400 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 40 heavy %A
4, 15 heavy % kaolin, 35 heavy %Al
2O
3, and the auxiliary agent ZJ of 2 heavy % magnesium additives (in MgO) and 8 heavy % zinc additives (in ZnO)
9
Embodiment 10
Get 2.75 kilograms of (butt) A
5With 1.4 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 100 grams, ZnO 150 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 50 heavy %A
5, 40 heavy %Al
2O
3, and the auxiliary agent ZJ of 2 heavy % magnesium additives (in MgO) and 3 heavy % zinc additives (in ZnO)
10
Embodiment 11
Get 1.5 kilograms of (butt) A
6, 1.5 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 150 grams, ZnO 100 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 30 heavy %A
6, 30 heavy % kaolin, 35 heavy %Al
2O
3, and the auxiliary agent ZJ of 3 heavy % magnesium additives (in MgO) and 2 heavy % zinc additives (in ZnO)
11
Embodiment 12
Get 1.25 kilograms of (butt) A
7, 1.5 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 100 grams, ZnO 400 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 25 heavy %A
7, 30 heavy % kaolin, 35 heavy %Al
2O
3, and the auxiliary agent ZJ of 2 heavy % magnesium additives (in MgO) and 8 heavy % zinc additives (in ZnO)
12
Embodiment 13
Get 2.25 kilograms of (butt) A
8With 1.65 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 250 grams, ZnO 250 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 45 heavy %A
8, 45 heavy %Al
2O
3, and the auxiliary agent ZJ of 5 heavy % magnesium additives (in MgO) and 5 heavy % zinc additives (in ZnO)
13
Embodiment 14
Get 1.75 kilograms of (butt) A
3, 1.25 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 50 grams, ZnO 200 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
3, 25 heavy % kaolin, 35 heavy %Al
2O
3, and the auxiliary agent ZJ of 1 heavy % magnesium additive (in MgO) and 4 heavy % zinc additives (in ZnO)
14
Embodiment 15
Get 1.75 kilograms of (butt) A
6, 1.25 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 50 grams, ZnO 200 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
6, 25 heavy % kaolin, 35 heavy %Al
2O
3, and the auxiliary agent ZJ of 1 heavy % magnesium additive (in MgO) and 4 heavy % zinc additives (in ZnO)
15
Embodiment 16
Get 1.75 kilograms of (butt) A
8, 1.25 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add the mixed aqueous solutions that 4.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride and zinc chloride and (wherein contain MgO 50 grams, ZnO 200 gram) and 2.79 kilograms of aluminium colloidal sols pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
8, 25 heavy % kaolin, 35 heavy %Al
2O
3, and the auxiliary agent ZJ of 1 heavy % magnesium additive (in MgO) and 4 heavy % zinc additives (in ZnO)
16
Comparative Examples 1
This Comparative Examples explanation with the ZRP-5 zeolite as active ingredient, contain the preparation of the contrast cracking additive of magnesium additive and zinc additive simultaneously.
Press the method preparation contrast auxiliary agent of embodiment 1, adopt the ZRP-5 zeolite of same weight to replace A
1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin, 30 heavy %Al
2O
3, and the contrast cracking additive CB of 1 heavy % magnesium additive (in MgO) and 4 heavy % zinc additives (in ZnO)
1
Comparative Examples 2
The explanation of this Comparative Examples is with modified zsm-5 zeolite (sample A
1) as active ingredient, do not contain the preparation of the contrast cracking additive of magnesium, zinc additive.
Get 1.75 kilograms of (butt) A1,1.5 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 30 heavy % kaolin and 35 heavy %Al
2O
3Contrast cracking additive CB
2
Comparative Examples 3
The explanation of this Comparative Examples is with modified zsm-5 zeolite (sample A
1) as the preparation of the contrast cracking additive of active ingredient, Mg-containing additive.
Get 1.75 kilograms of (butt) A
1, 1.35 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, adding the aqueous solution (wherein containing MgO 150 grams) and 2.79 kilograms of aluminium colloidal sols that 7.2 kilograms of decationized Y sieve water, 3 liters contain magnesium chloride pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 27 heavy % kaolin, 35 heavy %Al
2O
3, and the contrast cracking additive CB of 3 heavy % magnesium additives (in MgO)
3
Comparative Examples 4
The explanation of this Comparative Examples is with modified zsm-5 zeolite (sample A
1) as active ingredient, contain the preparation of the contrast cracking additive of zinc additive.
Get 1.75 kilograms of (butt) A
1, 1.35 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, adding the aqueous solution (wherein containing ZnO 150 grams) and 2.79 kilograms of aluminium colloidal sols that 7.2 kilograms of decationized Y sieve water, 3 liters contain zinc chloride pulled an oar 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 27 heavy % kaolin, 35 heavy %Al
2O
3, and the contrast cracking additive CB of 3 heavy % zinc additives (in ZnO)
4
Embodiment 17～32
These embodiment are example with the fixed fluidized-bed reactor, and the reaction result of cracking additive provided by the invention is described.
Respectively with 30 gram ZJ
1-ZJ
16Under 800 ℃, 100% steam atmosphere condition, carry out 8 hours burin-in process.Get the ZJ through burin-in process of different amounts
1-ZJ
16Mix with the industrial FCC equilibrium catalyst (the industrial trade mark is the FCC equilibrium catalyst of MLC-500, and main character sees Table 1) of different amounts, obtain catalyst mixture.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, stock oil is carried out catalytic cracking (stock oil character sees Table 2).
Table 3, table 4 and table 5 have been listed the composition of different catalysts mixture, cracking reaction condition and reaction result data.
Comparative Examples 5～9
These Comparative Examples are example with the fixed fluidized-bed reactor, and the reaction result that uses the contrast cracking additive is described.
By the method among the embodiment 17 same stock oil is carried out catalytic cracking reaction, different is that catalyst system therefor is respectively 100% industrial FCC equilibrium catalyst, contrast cracking additive CB
1～CB
4Mixture with industrial FCC equilibrium catalyst.
Listed file names with the composition of the catalyst mixture of different contrast cracking additives in the table 3, cracking reaction condition and reaction result data.
From the data of table 3, table 4 and table 5 as can be seen, compare with the contrast cracking additive, cracking additive provided by the invention can not only increase the catalytic cracking liquefied gas yield effectively, improve the octane value of catalytically cracked gasoline, can also obviously improve the density of propylene in the catalytic cracking liquefied gas simultaneously.
Table 1
Table 2
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101028157A CN100389176C (en) | 2004-12-28 | 2004-12-28 | A cracking aid for increasing propylene production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101028157A CN100389176C (en) | 2004-12-28 | 2004-12-28 | A cracking aid for increasing propylene production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1796498A CN1796498A (en) | 2006-07-05 |
| CN100389176C true CN100389176C (en) | 2008-05-21 |
Family
ID=36817820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004101028157A Expired - Lifetime CN100389176C (en) | 2004-12-28 | 2004-12-28 | A cracking aid for increasing propylene production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100389176C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101204668B (en) * | 2006-12-19 | 2011-12-28 | 石大卓越科技股份有限公司 | Propylene production increasing cracking catalyst and preparation method thereof |
| CN101683621B (en) * | 2008-09-28 | 2012-01-25 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed |
| CN102188992B (en) * | 2011-03-18 | 2012-11-07 | 任丘市华北石油科林环保有限公司 | Catalytic cracking assistant for propylene production increase for refinery FCC (fluidized catalytic cracking) device and preparation method thereof |
| CN102851058B (en) * | 2011-06-30 | 2015-05-20 | 中国石油天然气股份有限公司 | Method for improving octane number of catalytic cracking gasoline |
| CN103007990B (en) * | 2011-09-22 | 2014-12-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN107970990B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236880A (en) * | 1989-12-11 | 1993-08-17 | W. R. Grace & Co.-Conn. | Catalyst for cracking of paraffinic feedstocks |
| US20020049133A1 (en) * | 1999-03-02 | 2002-04-25 | Michael S. Ziebarth | High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith |
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | A Molecular Sieve with MFI Structure Containing Phosphorus and Transition Metals |
-
2004
- 2004-12-28 CN CNB2004101028157A patent/CN100389176C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236880A (en) * | 1989-12-11 | 1993-08-17 | W. R. Grace & Co.-Conn. | Catalyst for cracking of paraffinic feedstocks |
| US20020049133A1 (en) * | 1999-03-02 | 2002-04-25 | Michael S. Ziebarth | High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith |
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | A Molecular Sieve with MFI Structure Containing Phosphorus and Transition Metals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1796498A (en) | 2006-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100425534C (en) | Modified beta zeolite | |
| EP2075068B1 (en) | A catalyst for converting hydrocarbons | |
| CN105013525B (en) | A kind of assistant for calalytic cracking for improving low-carbon olefin concentration and preparation method thereof | |
| CN100389174C (en) | A cracking aid for increasing the concentration of propylene | |
| JP5053098B2 (en) | Catalyst and method for cracking hydrocarbons | |
| CN103785456B (en) | A cracking aid for increasing the concentration of low-carbon olefins | |
| CN103007989B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN103007990B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN103785458B (en) | A cracking aid for increasing the concentration of low-carbon olefins | |
| CN100537030C (en) | A catalytic cracking additive for increasing propylene concentration in liquefied gas | |
| CN102847551B (en) | Cracking aid for improving lower-carbon olefin concentration | |
| CN103007986A (en) | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration | |
| CN104998681B (en) | A kind of assistant for calalytic cracking for improving low-carbon olefin concentration and preparation method thereof | |
| CN104946301B (en) | A kind of catalysis conversion method for improving low-carbon olefin concentration | |
| CN103785457B (en) | A cracking aid for increasing the concentration of low-carbon olefins | |
| CN100389176C (en) | A cracking aid for increasing propylene production | |
| CN103785455B (en) | A cracking aid for increasing the concentration of low-carbon olefins in catalytic cracking | |
| CN100389175C (en) | Catalytic assistant for increasing propylene concentration in catalytic cracking liquefied gas | |
| CN103007991B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN100497530C (en) | Method for cracking hydrocarbon oil | |
| CN100351345C (en) | Method for catalytic cracking petroleum hydrocarbon | |
| CN103007993B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN103007992B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN104998677B (en) | A kind of assistant for calalytic cracking for improving low-carbon olefin concentration and preparation method thereof | |
| JPS63270546A (en) | Catalyst for conversion of hydrocarbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20080521 |