CN1112248C - Preparation of superstable Y-type molecular sieve - Google Patents
Preparation of superstable Y-type molecular sieve Download PDFInfo
- Publication number
- CN1112248C CN1112248C CN 99125504 CN99125504A CN1112248C CN 1112248 C CN1112248 C CN 1112248C CN 99125504 CN99125504 CN 99125504 CN 99125504 A CN99125504 A CN 99125504A CN 1112248 C CN1112248 C CN 1112248C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- salt
- ammonium
- weight
- rare earth
- 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 - Fee Related
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 101
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 44
- 235000019270 ammonium chloride Nutrition 0.000 claims description 22
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 238000003756 stirring Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- -1 rare earth chloride Chemical class 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 18
- 238000010792 warming Methods 0.000 description 17
- 238000005342 ion exchange Methods 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
本发明公开了一种超稳Y型分子筛的制备方法，是以氧化钠含量大于10(重)%的Y型分子筛为原料，按照分子筛∶铵盐∶金属盐∶氧化钛∶混合氯化稀土＝1∶0.2～2∶0.01～0.5∶0～0.2∶0～0.1的重量比，将分子筛、铵盐溶液、金属盐溶液、氧化钛、混合氯化稀土混合均匀，在PH值为3.8-10.8，20-90℃下搅拌0.5-4小时，经过滤、洗涤后在550-750℃、100%的水蒸气气氛中焙烧0.5-4小时。此方法可缩短工序，增加超稳Y型分子筛的产量，降低生产成本。The invention discloses a preparation method of an ultra-stable Y-type molecular sieve, which uses a Y-type molecular sieve with a sodium oxide content greater than 10 (weight)% as a raw material, according to molecular sieve: ammonium salt: metal salt: titanium oxide: mixed rare earth chloride = 1: 0.2～2: 0.01～0.5: 0～0.2: 0～0.1 weight ratio, the molecular sieve, ammonium salt solution, metal salt solution, titanium oxide, mixed rare earth chloride are evenly mixed, and the pH value is 3.8-10.8, Stir at 20-90°C for 0.5-4 hours, filter and wash, then bake at 550-750°C and 100% water vapor atmosphere for 0.5-4 hours. The method can shorten the process, increase the output of the ultra-stable Y-type molecular sieve, and reduce the production cost.
Description
The invention relates to a kind of preparation method of super-stable Y molecular sieves.
In modern petroleum refining industry, along with the wide material sources of crude oil type with to the variation of oil fuel kind demand, and the proposition of the friendly oil fuel prescription of environmental protection, people have proposed more and more higher requirement to being used for the refining of petroleum catalyzer.In order to satisfy multiple class, multi-level different requirements to catalyzer, prepare suitable oil or petrochemical industry catalyzer, people have carried out many modification work to the catalyzer constituent element.
Y zeolite has regular crystalline structure, and the positively charged ion of pore structure, bigger serface, balance skeleton electric charge can be substituted isostructuralism matter uniformly, is highly effective catalyzer constituent element.
Super-stable Y molecular sieves (brief note for USY) is the product that people carry out modification to Y zeolite, and because of the structure super stabilizing, the thermostability height has good selectivity and becomes various oil or petrochemical process activity of such catalysts constituent element more and more.
The preparation method of super-stable Y molecular sieves has hydrothermal method, EDTA complexometry, silicon tetrachloride dealumination complement silicon method, ammonium silicofluoride aluminium-eliminating and silicon-replenishing method and hydro-thermal acidic treatment etc.USP3293172, USP3402996, USP3449070 at first disclose high-temperature vapor and have handled Y zeolite to obtain the method for super-stable Y molecular sieves, and this also is the method for the present industrial preparation USY that extensively adopts both at home and abroad.The primary feature of super stabilizing is that structure cell shrinks, and with respect to original NaY molecular sieve, its shrinkage amplitude is 1.0～1.5%.If sodium content in the NaY molecular sieve (in sodium oxide weight) height, then structure cell shrinks few; Sodium content is low, and then the amplitude of structure cell contraction is big.
In the process of Hydrothermal Preparation USY molecular sieve, in order to reduce sodium content to 0.5 (weight) below the %, shrink to obtain bigger structure cell, generally all need the NaY molecular sieve is carried out several times ammonium ion exchange and hydrothermal calcine, after being ion-exchange of NaY molecular sieve through ammonium and filtration, carry out hydrothermal calcine again.So repeat the process of ion-exchange and hydrothermal calcine, respectively once claim " one hands over a roasting ", respectively carry out twice title " two hand over two roastings ", hand over a roasting method as adopting two among the EP667185A1, CN1031030A, CN1060977A etc. adopt two to hand over two roasting methods.
Do not see so far at original NaY molecular sieve and adopt one to hand over the method for a roasting to make molecular sieve have big structure cell to shrink and keep the report of high crystallization reservation degree, do not see the report of when one hands over a roasting, in ultra-steady Y molecular sieve, introducing metallic element yet.
The objective of the invention is to provide on the basis of existing technology a kind of preparation method than the more simple containing metal super-stable Y molecular sieves of prior art.
Method provided by the invention be with Y zeolite in ammonium ion exchange, add metal ion solution and also carry out hydrothermal calcine.
According to method provided by the invention, the concrete steps of preparation super-stable Y molecular sieves are as follows: is raw material with sodium oxide content greater than the Y zeolite of 10 (weight) %, according to molecular sieve: ammonium salt: metal-salt: titanium oxide: the weight ratio of mixed chlorinated rare earth=1: 0.2～2: 0.01～0.5: 0～0.2: 0～0.1, with molecular sieve, ammonium salt solution, metal salt solution, titanium oxide, mixed chlorinated rare earth mixes, at pH value is 3.8～10.8,20-90 ℃ was stirred 0.5-4 hour down, after filtration, the washing back is at 550～750 ℃, in 100% the steam atmosphere roasting 0.5-4 hour, wherein said metal-salt was selected from Al, Ba, Ca, Mg, Sr, Sn, Sb, Zn, one of the salt of metals such as Zr or the mixture of two or more metal-salt wherein.
Said ammonium salt can be selected from ammonium chloride, ammonium sulfate or ammonium nitrate, wherein preferred ammonium chloride.
The optimum ratio of said molecular sieve, ammonium salt, metal-salt, titanium oxide, mixed chlorinated rare earth is 1: 1.0～1.8: 0.1～0.3: 0～0.1: 0～0.07.
The pH value preferable range is 5.0～7.0, and general available ammoniacal liquor or hydrochloric acid are regulated.
Adopt ordinary method to carry out the molecular sieve of a friendship one roasting Hydrothermal Preparation, though its structure cell has certain contraction, more than 24.50 , crystallization reservation degree is below 87% basically; Adopt two of ordinary method to hand over the USY molecular sieve of two roasting Hydrothermal Preparation, though its lattice constant below 24.5 , crystallization reservation degree has only about 70%.And method provided by the invention is to NaO
2Content has been taked in ammonium ion exchange greater than the Y zeolite of 10 (weight) %, the technical measures that also exchange with molecular sieve with the metal ion of IIA, IIIA, IVA, VA, IIB, IVB family, only carry out hydrothermal calcine one time, just can reach conventional hydrothermal method two and hand over just accessible structure cell shrinkage amplitude of two roastings, lattice constant is less than 24.48 , and crystallization reservation degree is higher, can remain on more than 90%.Therefore, method provided by the invention has shortened operation, can increase the output of USY, reduces production costs.
The USY molecular sieve that the inventive method is prepared, as the catalyzer constituent element, not only have ultra-steady Y molecular sieve inherent high hydrothermal stability, but also can provide owing to introducing other catalytic performance that metal ion brings, to satisfy the needs of different oil or petrochemical process.As contain the USY of Mg, Ca, Sr, Ba, can be used as anti-vanadium catalyst constituent element in the catalytic cracking process; The USY that contains metal ions such as Mg, Ca, Zn, Al can be used as catalytic reforming and isomerization catalyst constituent element and uses; Introduce the USY of above-mentioned metal ion and rare earth element, can be applied to the alkylated reaction of benzene; Introduce the USY of Zn, in shortening, also have the effect of removing the impurity nitride; Introduce the USY of Zr, can be used in the reactions such as decomposition of hydrocarbons, isomerization, alkylation.
Following example will be described further USY molecular sieve preparation method provided by the invention.
In the example in the molecular sieve content of sodium oxide, aluminum oxide and silicon-dioxide measure by 3271 type fluorescence analysers, the lattice constant of molecular sieve and crystallization reservation degree are measured by SIEMENS D5005D X-ray diffractometer, wherein:
Used NaY molecular sieve is the catalyst plant production of Qilu Petrochemical company, sodium oxide content 14 (weight) %, and silica alumina ratio 4.9, degree of crystallinity is 93%.
Agents useful for same is the chemically pure reagent that the Beijing Chemical Plant produces, and wherein ammonia concn is 25～28 (weight) %.
Used mixed chlorinated rare earth (RECl
x) produce by Inner Mongol Baotou rare earth factory, content of rare earth is counted 46 (weight) %, wherein La with rare earth oxide
2O
3=24.5 (weight) %, Ce
2O=6.0 (weight) %, Pr
6O
3=6.0 (weight) %, Nd
2O
3=9.5 (weight) %.Use preceding through 800 ℃ of roastings 1 hour.
Example 1
Get 50 gram NaY molecular sieves, be dispersed in the ammonium chloride solution of 200 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the magnesium chloride hexahydrate solution that adds 60 grams 20% (in magnesium chloride weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.5, is warming up to 90 ℃, stirs 2 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 600 ℃, the water vapour of feeding 100%, after the roasting 2 hours, with 20 times of deoxidation deionised water, oven dry, obtain the USY molecular sieve, numbering A.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Comparative Examples 1
Get 50 gram NaY molecular sieves, be dispersed in the ammonium chloride solution of 200 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the pH value of regulating the gained slurries with ammoniacal liquor is 6.5, is warming up to 90 ℃, stirs exchange 2 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 600 ℃, the water vapour of feeding 100%, roasting 2 hours obtains the USY molecular sieve, numbering A '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 2
Getting 60 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 340 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the four water-calcium nitrate solution that adds 50 grams 25% (in nitrocalcite weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.0, be warming up to 85 ℃, stir exchange 2.5 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 640 ℃, the water vapour of feeding 100%, roasting is after 2 hours, with 20 times of deoxidation deionised water, oven dry obtains USY molecular sieve B.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Comparative Examples 2
Press the method preparation contrast molecular sieve for preparing molecular sieve B in the example 2, do not add ca nitrate soln when being ion-exchange, the molecular sieve that makes note is made B '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 3
Get 50 gram NaY molecular sieves and be dispersed in the ammonium chloride solution of 200 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, add the alum liquor of 50 grams 11.2% (in Tai-Ace S 150 weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.8, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 700 ℃, feed 100% water vapour, roasting is after 1.5 hours, with 20 times of deoxidation deionised water, oven dry,, the molecular sieve numbering C that obtains.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 3
Press the method preparation contrast molecular sieve for preparing molecular sieve C in the example 3, do not add alum liquor when ion-exchange, the molecular sieve that obtains is numbered C '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Example 4
Getting 50 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 150 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the zinc nitrate hexahydrate solution that adds 75 grams 30% (in zinc nitrate hexahydrate weight), the pH value of regulating the gained slurries with ammoniacal liquor is 5.2, be warming up to 80 ℃, stir exchange 2 hours, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 620 ℃, feed 100% water vapour, roasting is after 2 hours, with 20 times of deoxidation deionised water, oven dry, the molecular sieve that obtains, numbering D.
Comparative Examples 4
Press the method preparation contrast molecular sieve for preparing molecular sieve D in the example 4, do not add zinc nitrate solution when ion-exchange, the molecular sieve that obtains is numbered D '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Example 5
Getting 80 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 360 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the two water zirconium nitrate solutions that add 40 grams 20% (in two water zirconium nitrate weight), the magnesium chloride hexahydrate solution of 40 grams 20% (in magnesium chloride weight), the pH value of regulating slurries with ammoniacal liquor is 6.5, is warming up to 85 ℃, stirs exchange 2.0 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 660 ℃, the water vapour of feeding 100%, after the roasting 2 hours, with 20 times of deoxidation deionised water, oven dry, obtain the USY molecular sieve, numbering E.
The chemical constitution and the structural parameter of this molecular sieve of gained see Table 1.
Comparative Examples 5
Press the method preparation contrast molecular sieve for preparing molecular sieve E in the example 5, just when ion-exchange, do not add two water zirconium nitrate solutions and magnesium chloride hexahydrate solution, the molecular sieve that obtains, numbering E '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 6
Getting 65 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 300 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the two water zirconium nitrate solutions that add 40 grams 20% (in two water zirconium nitrate weight), the re chloride that adds 15 grams 41.39% (mixed chlorinated rare earth weight meter), the pH value of regulating the gained slurries with ammoniacal liquor is 6.5, is warming up to 85 ℃, stirs exchange 2.0 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 680 ℃, the water vapour of feeding 100%, after the roasting 2.5 hours, with 20 times of deoxidation deionised water, oven dry, obtain the USY molecular sieve, numbering F.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Comparative Examples 6
Press the method preparation contrast molecular sieve for preparing molecular sieve F in the example 6, just do not add two water zirconium nitrate solution and re chlorides when ion-exchange, the molecular sieve that obtains is numbered F '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 7
Getting 80 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 360 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the two water zirconium nitrate solutions that add 25 grams 20% (in two water zirconium nitrate weight), the Adlerika of 30 grams 35% (in sal epsom weight), the mixed chlorinated rare earth solution that adds 10 grams, 41.39 heavy % (in mixed chlorinated rare earth weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.8, be warming up to 90 ℃, stir exchange 2.5 hours, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 700 ℃, feed 100% water vapour, roasting is after 1.5 hours, with 20 times of deoxidation deionised water, oven dry obtains the USY molecular sieve, numbering G.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 7
Press the method preparation contrast molecular sieve for preparing molecular sieve G in the example 7, do not add two water zirconium nitrate solutions, Adlerika and mixed chlorinated rare earth solution when ion-exchange, the molecular sieve that obtains is numbered G '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Example 8
Getting 70 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 310 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the titanium dioxide suspension liquid that adds 15 grams 30% (in titanium dioxide weight), the Adlerika of 40 grams 35% (in sal epsom weight), the mixed chlorinated rare earth solution that adds 10 grams 41.39% (in mixed chlorinated rare earth weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.0, be warming up to 90 ℃, stir exchange 2.0 hours, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 680 ℃, feed 100% water vapour, roasting is after 2.5 hours, with 20 times of deoxidation deionised water, oven dry obtains the USY molecular sieve, numbering H.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 8
Press the method preparation contrast molecular sieve for preparing molecular sieve H in the example 8, just do not add Adlerika, titanium dioxide suspension liquid and re chloride when ion-exchange, the molecular sieve that obtains is numbered H '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 9
Get the molecular sieve G ' of preparation in the Comparative Examples 7, replace the NaY molecular sieve, repeat the step of Comparative Examples 6, obtain two and hand over the molecular sieve of two roastings, be numbered G " with it.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
As can be seen from Table 1, the USY molecular sieve that the present invention prepares is compared with adopting a molecular sieve of handing over a roasting hydrothermal method to make, bigger structure cell shrink grading is not only arranged, and crystallization reservation degree is higher; In addition as can be seen, though hydrothermal method routinely increases the contrast molecular sieve that the number of times of ion-exchange and hydrothermal calcine makes and also can reach bigger structure cell shrink grading, crystallization reservations degree is more much lower than the molecular sieve that the inventive method prepares.
The chemical constitution of table 1 molecular sieve and structural parameter
| Example number | The molecular sieve numbering | Chemical constitution, heavy % | Structural parameter | ||||
| Na 2O | Al 2O 3 | SiO 2 | Metal (in oxide compound) | Lattice constant | Crystallization reservation degree % | ||
| 1 | A | 2.0 | 20.5 | 74.9 | Mg，2.6 | 24.42 | 90.8 |
| 2 | B | 2.2 | 22.8 | 72.0 | Ca，3.0 | 24.45 | 90.0 |
| 3 | C | 2.3 | 24.5 | 73.2 | Al | 24.43 | 90.2 |
| 4 | D | 2.4 | 22.9 | 73.7 | Zn，1.0 | 24.48 | 90.4 |
| 5 | E | 2.3 | 21.5 | 72.6 | Zr，1.8 Mg，1.8 | 24.46 | 91.2 |
| 6 | F | 2.0 | 23.0 | 72.6 | Zr，1.3 RE，1.3 | 24.48 | 90.2 |
| 7 | G | 2.1 | 22.2 | 72.7 | Zr，1.1 Mg，0.9 RE，1.0 | 24.45 | 90.4 |
| 8 | H | 2.2 | 22.4 | 73.2 | Mg，0.7 Ti，0.7 RE，0.8 | 24.47 | 90.4 |
| Comparative Examples 1 | A’ | 2.8 | 23.6 | 74.6 | - | 24.54 | 84.7 |
| Comparative Examples 2 | B’ | 3.1 | 23.4 | 73.5 | - | 24.55 | 84.4 |
| Comparative Examples 3 | C’ | 2.9 | 24.1 | 73.0 | - | 24.51 | 84.8 |
| Comparative Examples 4 | D’ | 3.0 | 24.1 | 73.9 | - | 24.53 | 86.9 |
| Comparative Examples 5 | E’ | 3.1 | 24.4 | 73.5 | - | 24.52 | 80.8 |
| Comparative Examples 6 | F’ | 3.2 | 23.7 | 73.1 | - | 24.52 | 84.2 |
| Comparative Examples 7 | G’ | 3.0 | 23.5 | 73.5 | - | 24.51 | 85.6 |
| Comparative Examples 8 | H’ | 2.9 | 23.8 | 73.3 | - | 24.51 | 82.7 |
| Comparative Examples 9 | G” | 0.7 | 22.6 | 75.4 | - | 24.42 | 71.0 |
Claims (5)
1, a kind of preparation method of super-stable Y molecular sieves, it is characterized in that be raw material with sodium oxide content greater than 10 Y zeolites that weigh %, according to molecular sieve: ammonium salt: metal-salt: titanium oxide: the weight ratio of mixed chlorinated rare earth=1: 0.2～2: 0.01～0.5: 0～0.2: 0～0.1, with molecular sieve, ammonium salt solution, metal salt solution, titanium oxide, mixed chlorinated rare earth mixes, at pH value is 3.8-10.8,20-90 ℃ was stirred 0.5-4 hour down, after filtration, the washing back is at 550-750 ℃, in 100% the steam atmosphere roasting 0.5-4 hour, wherein said metal-salt was selected from Al, Ba, Ca, Mg, Sr, Sn, Sb, Zn, one of the metal-salt of Zr or the mixture of two or more metal-salt wherein.
2, in accordance with the method for claim 1, wherein said ammonium salt is selected from ammonium chloride, ammonium sulfate or ammonium nitrate.
3, in accordance with the method for claim 2, wherein said ammonium salt is an ammonium chloride.
4, in accordance with the method for claim 1, wherein said molecular sieve: ammonium salt: metal-salt: titanium oxide: the proportioning of mixed chlorinated rare earth is 1: 1.0～1.8: 0.1～0.3: 0～0.1: 0～0.07.
5, in accordance with the method for claim 1, wherein said pH value is 5～7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99125504 CN1112248C (en) | 1999-12-02 | 1999-12-02 | Preparation of superstable Y-type molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99125504 CN1112248C (en) | 1999-12-02 | 1999-12-02 | Preparation of superstable Y-type molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1297787A CN1297787A (en) | 2001-06-06 |
| CN1112248C true CN1112248C (en) | 2003-06-25 |
Family
ID=5283972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99125504 Expired - Fee Related CN1112248C (en) | 1999-12-02 | 1999-12-02 | Preparation of superstable Y-type molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1112248C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134576B (en) * | 2006-09-01 | 2010-09-08 | 中国石油大学(北京) | Method for Improving Hydrothermal Stability of Y Molecular Sieve Using Skeleton Heteroatoms |
| CA2867947C (en) * | 2013-10-22 | 2021-11-09 | Jun Long | A metal modified y zeolite, its preparation and use |
| CN106145152B (en) * | 2015-03-31 | 2018-06-19 | 中国石油化工股份有限公司 | Modified Y zeolite and its preparation method and application |
| CN106145153B (en) * | 2015-03-31 | 2018-06-19 | 中国石油化工股份有限公司 | Modified y zeolite and its preparation and application |
| CA3006197A1 (en) * | 2015-11-24 | 2017-06-01 | Basf Corporation | Fluid catalytic cracking catalysts for increasing butylene yields |
| CN108201898A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | A kind of method of Y-type molecular sieve modification |
| CN119320144B (en) * | 2024-12-13 | 2025-05-13 | 山东理工大学 | Rare earth-free Y-type molecular sieve for heavy oil catalytic cracking reaction and preparation method thereof |
-
1999
- 1999-12-02 CN CN 99125504 patent/CN1112248C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1297787A (en) | 2001-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1257769C (en) | A kind of MFI molecular sieve containing phosphorus and metal components and its application | |
| CN1034718C (en) | A kind of cracking catalyst and preparation method thereof | |
| CN1202007C (en) | A kind of preparation method of rare earth super stable Y molecular sieve | |
| CN1194181A (en) | Phosphorus containing molecular sieve with MFI structure | |
| CN1112248C (en) | Preparation of superstable Y-type molecular sieve | |
| CN1276873C (en) | A kind of preparation method of mordenite and beta zeolite mixed crystal material | |
| CN1096417C (en) | Synthesis method for beta zeolite | |
| CN1803612A (en) | Y molecular sieve modification method | |
| CN1102634C (en) | Catalyst for catalytic thermal cracking process to prepare lower olefine | |
| CN101353171B (en) | Method for synthesis of beta-zeolite | |
| CN1042201C (en) | Olefin-Prolific Cracking Catalysts | |
| CN1123535C (en) | Preparation process of beta-zeolite | |
| CN1676463A (en) | Method for preparing rare-earth ultrastable Y-type zeolite | |
| CN1060976A (en) | Preparation method of ultrastable Y-type zeolite containing amorphous alumina | |
| CN1094074C (en) | Toluene disproportionation and transalkylation catalyst and its process | |
| CN1317359C (en) | Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite | |
| CN1958452A (en) | Method for raising content of rare earth of ultra stable Y type zeolite | |
| CN1132898C (en) | Petroleum catalytic cracking catalyst | |
| CN86107531A (en) | Molecular sieves containing rare earth oxides and their preparation | |
| CN1024503C (en) | Rare earth Y molecular sieve cracking catalyst and its preparation | |
| CN1180059C (en) | Phosphorus-containing hydrocarbon cracking catalyst and its preparation | |
| CN1224667C (en) | Velocit cracking method | |
| CN1053918C (en) | Double zeolite catalyst for prepn. of low carbon olefine | |
| CN1165376C (en) | Faujasite molecular sieve composition and its preparing process | |
| CN1078821C (en) | Beta zeolite containing rare-earth and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030625 Termination date: 20181202 |