CN106927482B - Preparation method of ultrastable Y-type molecular sieve - Google Patents
Preparation method of ultrastable Y-type molecular sieve Download PDFInfo
- Publication number
- CN106927482B CN106927482B CN201511020516.3A CN201511020516A CN106927482B CN 106927482 B CN106927482 B CN 106927482B CN 201511020516 A CN201511020516 A CN 201511020516A CN 106927482 B CN106927482 B CN 106927482B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- iii
- ammonium
- 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.)
- Active
Links
- 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 213
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 210
- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 230000000737 periodic effect Effects 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 55
- 150000002910 rare earth metals Chemical class 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000012065 filter cake Substances 0.000 claims description 19
- 238000005342 ion exchange Methods 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical group [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-L 2-(carboxymethyl)-2-hydroxysuccinate Chemical compound [O-]C(=O)CC(O)(C(=O)O)CC([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-L 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 48
- 238000000034 method Methods 0.000 abstract description 26
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 25
- 238000001035 drying Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 14
- 238000004321 preservation Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- -1 rare earth ion Chemical group 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229910021536 Zeolite Inorganic materials 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
- 239000003921 oil Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052665 sodalite Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000012839 cake mixes Nutrition 0.000 description 1
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A process for preparing the ultrastable Y-type molecular sieve includes such steps as exchanging NaY molecular sieve with ammonium ion, filtering, mixing with the compound containing IIIB element in periodic table, drying and hydrothermal calcining. The Y-type molecular sieve IIIB element obtained by the method is not lost, the preparation process is simple, and the Y-type molecular sieve IIIB element has excellent activity, hydrothermal stability and heavy metal pollution resistance.
Description
Technical field
The present invention relates to a kind of preparation methods of super-stable Y molecular sieves, pass through spray drying mixing more particularly to one kind
Preparation method containing the super-stable Y molecular sieves of III B element in the periodic table of elements.
Background technique
Crude oil heaviness, in poor quality degree are increasingly sharpened, highly-efficient processing heavy oil, mix refining residual oil become oil refining enterprise improve plus
Work ability, the urgent need for obtaining more high profit.Catalytic cracking is the most important technique of processing of heavy oil, since its heavy oil conversion is imitated
Rate height, good product quality, non-hydrogen and the significant advantages such as operating pressure is low make it occupy act foot in refinery's processing heavy oil technique
The status of weight is the main source of oil plant profit.According to statistics, whole world catalytic cracking unit shares 420 sets or so at present,
Single set catalytic cracking unit is largest up to 10,000,000 tons/year, about 7.37 hundred million tons of total working ability, occupies the head of secondary operation
Position.
Due to being easy to produce the macromolecular compound of coke in heavy oil and residual oil containing colloid, asphalitine etc., and contain
Heavy metal nickel, vanadium etc. cause nickel content of vanadium on catalytic cracking equilibrium catalyst relatively common in 10000 μ g/g, and are up to
The serious pollution of 15000 μ g/g is not also rare, and vanadium seriously destroys the activity in catalyst under catalytic cracking high temperature thermal and hydric environment
The structure of component molecular sieve, causes catalyst activity to reduce, and catalytic cracking product distribution is made to be deteriorated.Therefore, it is necessary to develop to have
Excellent activity and hydrothermal stability, the molecular sieve simultaneously with preventing from heavy metal performance, to meet heavy oil, slag oil cracking to catalysis
The strict demand of agent performance.
In order to improve the activity and stability of molecular sieve, generally molecular sieve is changed using rare earth or phosphorus in the prior art
Property processing should if Chinese patent CN1169717 C discloses the method and product that a kind of Y zeolite is modified with rare earth ion
Method is raw material with NaY molecular sieve, is first exchanged through ammonium, then carries out hydro-thermal process, then with containing H+、NH4 +And RE3+Solution processing
Afterwards, washed, dry, roasting, obtains modified molecular screen product.Chinese patent CN1111136 C discloses a kind of phosphorous and dilute
Soil Y type molecular sieve preparation method, be that NaY molecular sieve is first used into ammonium ion and rare earth ion exchanged, roasted, then with phosphorus
The P of 1~10 weight % in compound reaction bonded2O5, then roasted to obtain.Chinese patent CN1209288 C discloses one kind
The preparation method of phosphorous and rare earth faujasite, is first once to be exchanged faujasite with ammonium compounds and phosphorus compound
After reaction, earth solution then is introduced in exchange slurries and is further reacted, is filtered, washed, then roasted to obtain.Containing this
The catalyst activity stability of zeolite is good, and yield of gasoline is high, and coke yield is low, heavy oil cracking ability and resistance to heavy metal pollution
By force.Chinese patent CN1026225 C discloses a kind of preparation method of rare-earth Y molecular sieve, is by NaY molecular sieve and rare earth ion
After carrying out ion exchange in aqueous solution, filtering, filter cake is roasted to obtain in flowing water steam.Chinese patent
CN1069553 C discloses a kind of method for preparing rare earth Y type molecular sieve, is that NaY molecular sieve and rare earth ion are carried out ion
After exchange, filtering, filter cake is roasted again, and 1~40% of the product after roasting is recycled back into next group rare earth exchanged slurries
The operation is continued the above, remaining is used to prepare catalyst as REY zeolite product, is so carried out continuously, and obtains Rare Earth Y
Type molecular sieve.Chinese patent CN103058217 A discloses a kind of preparation method of Y molecular sieve containing rare earth, this method NaY
Molecular sieve is raw material, is first exchanged through ammonium, then carries out hydro-thermal process, then with containing H+、NH4 +And RE3+It is molten with the mixing of organic solvent
After liquid processing, mother liquor separation, filter cake roasting obtain modified molecular screen product.Chinese patent CN1159101 C discloses one kind and contains
The preparation method of hyperastable Y-type RE zeolite, the overstable gamma zeolite and a kind of rare earth that sodium oxide content is 3~5 weight % by this method
Polymer solution mixing, is made a kind of slurries, by obtained slurries in shear stress at least 10 kilograms per centimeters2Under conditions of be ground to
It is 1 minute few, obtain modified molecular screen product.The zeolite of this method preparation has high hydrothermal stability, activity stability, anti-sodium
And the ability of preventing from heavy metal pollution.
Existing Y type molecular sieve technology of preparing, solves the deficiency of molecular sieve some aspects, meets molecular sieve catalyst
Demand in some aspects, but the prior art obtains molecular sieve, work by repetitious ion exchange, filtering, calcination process
Skill is complicated, and molecular sieve yield is low；After the rare earth ion exchanged of molecular sieve, general by filtering, filter cake carries out calcination process, this
Sample, which results in rare earth, all to exchange to molecular sieve up, and a part of rare earth enters filtrate and is lost, rare earth utilization rate
It is not high.The prior art just carries out hydrothermal calcine before rare earth exchanged, causes molecular sieve structure to destroy more, molecular sieve activity
Decline.Rare earth is introduced in the solution after phosphorus exchange, the sediment of phosphoric acid rare earth easy to form makes rare earth that can not play stabilization
The purpose of molecular sieve structure can not play the role of good preventing from heavy metal pollution.Repeatedly by the molecular sieve after roasting
The 1~40% of product is recycled back into the operation for continuing processing in next group rare earth exchanged slurries, causes system with molecular sieve for preparing for work
The problems such as skill complexity, energy waste and molecular sieve yield reduce.In addition, can be brought during system with molecular sieve for preparing is standby using organic solvent
New problem of environmental pollution.Therefore, it is wanted to meet molecular sieve to activity, hydrothermal stability and resistance to heavy metal pollution
It asks, reduces the preparation cost and complex process degree of molecular sieve, despite recent molecular sieve technology of preparing, but there is still a need for systems
Standby simple process, the III B element utilization rate such as rare earth is high or does not lose, while having excellent activity, hydrothermal stability and anti-heavy
The molecular sieve new preparation technology of metallic pollution.
Summary of the invention
The object of the invention is that avoiding the deficiency of above-mentioned technology, a kind of system with molecular sieve for preparing different from existing method is provided
Preparation Method, the resulting Y type molecular sieve preparation process of the method for the present invention, preparation process is simple, and III B element is not lost, system with molecular sieve for preparing
Standby technology is more environmentally-friendly, while resulting Y type molecular sieve has excellent activity, hydrothermal stability and preventing from heavy metal pollution
Energy.
In order to achieve the object of the present invention, the present invention provides a kind of preparation method of modified super-stable Y molecular sieves, feature
It is that preparation method includes first exchanging NaY molecular sieve with ammonium ion, the change containing III B element in the periodic table of elements is mixed after filtering
Object is closed, without filtering, directly carries out spray drying and hydrothermal calcine, obtains modified super-stable Y molecular sieves.
Realize that the specific technical solution of the present invention can be with are as follows:
(1), NaY molecular sieve and ammonium salt solution are subjected to ion exchange, water and molecular sieve (in terms of butt) weight ratio 2~30
: 1, pH=2.8~6.5,5~100 DEG C of temperature, swap time 0.3~3.5 hour, preferably pH=2.8~5.0, temperature 60~
100 DEG C, swap time 0.5~2.5 hour；Filtering, after Washing of Filter Cake with water, the compound containing III B element in the periodic table of elements
Mixing, it is not washed to be directly spray-dried, obtain the molecular sieve containing III B element in the periodic table of elements；
(2), in roaster, by the resulting molecular sieve containing III B element in the periodic table of elements of step (1) in 10 weight %
Hydrothermal calcine is carried out under~100 weight % water vapour atmospheres, 450~700 DEG C of maturing temperature, calcining time 0.5~4 hour, is obtained
To modified super-stable Y molecular sieves.
In molecular sieve, the distribution of III B element is different in the periodic table of elements, and the influence to molecular sieve performance is different,
Wherein, III B elements on molecular sieve are mostly exchanged in the form of an ion in the prior art, molecule can be entered during hydrothermal calcine
In the small cage of sieve, molecular sieves stabilized crystal structure provides more acid activity centers.Inventors be surprised to learn that with independent phase shape
III B element existing for formula, can trap heavy metals vanadium, form stable vanadate, avoid vanadium destroy molecular sieve crystal structure,
Have the function that preventing from heavy metal pollution.Therefore the present invention does not have after the compound of III B element in addition element periodic table dexterously
There is washing process, it is different from common exchange process in the prior art, keep the utilization rate of III B element in the periodic table of elements high or not
Loss, and molecular sieve is prepared using the method for the present invention, the compound of III B element during mixing, roasting with molecular sieve,
A part carries out ion exchange with the sodium on molecular sieve in the form of an ion, and another part is present in molecular sieve in the form of independent phase
Surface, therefore, the molecular sieve of the technology of the present invention preparation, crystal structure that can be molecular sieves stabilized have excellent activity and water
Thermal stability, and have the function of trap heavy metals, preventing from heavy metal pollution.
The preparation method of molecular sieve of the present invention passes through the change of III B element in the periodic table of elements in rate-determining steps (1)
The type and filter cake of conjunction object and compound incorporation time, mixed proportion containing III B element in the periodic table of elements, reach adjusting point
The purpose of the distribution of III B element in son sieve, can be according to the reality to molecular sieve activity, stability and preventing from heavy metal pollution
Need, adjust exist in the form of an ion and in the form of independent phase existing for III B element ratio.Filter cake with containing in the periodic table of elements
The compound of III B element is preferably according to molecular sieve (in terms of butt): water: compound (oxide meter) weight ratio of III B element is 1
: 2~8: 0.001~0.20 ratio mixing, preferably 1: 2~4: 0.01~0.15 ratio mixing, is preferably 60 in temperature
~100 DEG C, stirring best 0.5~1.5 hour or more, it is not washed be directly spray-dried, hydrothermal calcine, resulting molecule
In sieve, III B element a part exchanges on molecular sieve in the form of an ion, and the whipping temp the high more is conducive to III B element with ion
Form exchanges to molecular sieve up, and wherein other part does not exchange to III B element that molecular sieve gets on, in subsequent step (2)
Hydrothermal calcine during, a part by migration of solid phases enters molecular sieve, plays work identical with III B element of ion exchange
With another part exists in the form of independent phase, may be configured to trap heavy metals during catalytic cracking reaction.In step (1)
In, when the type of the compound of III B element in the periodic table of elements being mixed into molecular sieve is water-soluble compound and is divided
The mixed proportion of son sieve it is relatively low (such as molecular sieve (in terms of butt): compound (oxide meter) weight ratio of III B element is 1:
0.001~0.09 ratio mixing) when, this III B element largely exchanges on molecular sieve in the form of an ion, plays raising point
The effect of son sieve activity and hydrothermal stability, small part in addition exist in the form of independent phase, can play catalytic cracking reaction mistake
The effect of trap heavy metals in journey.In step (1), when the chemical combination of III B element in the periodic table of elements being mixed into molecular sieve
When the type of object is carbonate not soluble in water, oxide, hydroxide, the compound of this III B element is in subsequent step (2)
Hydrothermal calcine during, enter molecular sieve at least partially through migration of solid phases, play work identical with III B element of ion exchange
With major part in addition exists in the form of independent phase, can play the role of trap heavy metals during catalytic cracking reaction.Pass through
Control in the water-soluble and not soluble in water periodic table of elements different proportion of the compound of III B element and its in molecular sieve
Introduction volume, in adjustable molecular sieve by ion exchange form and in the form of independent phase existing for III B element different proportion and
Content, to need to prepare molecular sieve according to active and preventing from heavy metal pollution.
The preparation method of molecular sieve of the present invention, wherein the ammonium salt in step (1) be selected from ammonium sulfate, ammonium hydrogen sulfate,
Ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, ammonium citrate, ammonium dihydrogen citrate, one in diammonium hydrogen citrate
Kind is a variety of, and ammonium salt is mainly used for exchanging the sodium on Y type molecular sieve, makes the sodium oxide content of the molecular sieve after exchange 2
Within the scope of~6 weight %.
The preparation method of molecular sieve of the present invention, wherein III B element is selected from scandium, yttrium, lanthanide series rare-earth elements
One of or it is a variety of.The lanthanide rare is lanthanum rich rare earth, cerium-rich rare earth, pure lanthanum or pure cerium.Contain III in step (1)
The compound of B element is selected from the change of the halide, nitrate, carbonate, oxide, hydroxide, rich III B element of III B element
One of object or a variety of is closed, step can be adjusted according to the actual needs to molecular sieve activity, stability and preventing from heavy metal pollution
Suddenly in (1) the different compounds of these III B elements ratio.
The preparation method of molecular sieve of the present invention, wherein it is described the step of (2) roasting process, be by step (1)
The resulting molecular sieve containing III B element in the periodic table of elements carries out hydrothermal calcine under 100% water vapour atmosphere.Roasting process
In, there are dealuminzations and silicon migration, so that the Si-O-Al on framework of molecular sieve is replaced by Si-O-Si, due to Si atom (diameter
Smaller than Al atom (diameter 0.1nm) for 0.082nm), bond distance shortens (Si-O bond distance 0.161nm, Al-O bond distance 0.174nm),
Structure cell is shunk, and molecular sieve structure stability improves.In roasting process, simultaneous Ion transfer, wherein in the periodic table of elements
Na of the Ion transfer of III B element to II position S I and S in molecular sieve sodalite cage, in sodalite cage+Then move to supercage
In, molecular sieve is detached from subsequent ion exchange process.Compared with simple high-temperature roasting, under 100% water vapour atmosphere
Hydrothermal calcine is carried out, above-mentioned III B element ion and Na are more advantageous to+The migration of ion is more favorable to keep molecular sieve
Crystal structure and structure cell are shunk.
III B element (in terms of the oxide) content of super-stable Y molecular sieves of the present invention is 0.1~20 weight %, oxygen
Change sodium content is 2~6 weight %.
It should be noted that by the way of spray drying, making III B element after the compound of molecular sieve III B element of mixing
Load over a molecular sieve is more evenly；Molecular sieve ion exchange of the present invention drop sodium, after mixing the compound of III B element, molecular sieve
In sodium oxide molybdena still containing 2~6 weight %, carried out hydrothermal calcine processing after mixing the compound of III B element due to molecular sieve,
During hydrothermal calcine, the Ion transfer of III B element into molecular sieve sodalite cage, meanwhile, in ion exchange process not
The Na being easy in the sodalite cage exchanged by ammonium salt+Ion then moves in supercage, Na+Ion makes it very there are the change of position
It is easy after being prepared into the microspherical catalyst containing molecular sieve, ion exchange is carried out by ammonium salt etc., is detached from molecular sieve catalyst.This
Simplify the preparation process of molecular sieve, but the performance of molecular sieve catalyst will not be adversely affected.
Main advantages of the present invention and effect:
The present invention first exchanges NaY molecular sieve with ammonium ion, makes the sodium oxide content of NaY molecular sieve in 2~6 weight % ranges
Interior, after filtering, filter cake mixes the compound containing III B element in the periodic table of elements, then not washed to be directly spray-dried
And hydrothermal calcine, obtain super-stable Y molecular sieves.The preparation process of this molecular sieve is simple, does not need that ion exchange is repeated
And roasting, III B element exists in the form of ion exchange and two kinds of independent phase in molecular sieve, and it is living to each serve as raising molecular sieve
The ratio of property, the purpose of stability and preventing from heavy metal performance, III B element existing for both forms is adjustable.Due to mixing III B member
After element, without being filtered, washed for molecular sieve, but Direct spraying is dry, therefore III B element is not lost, and makes the system of molecular sieve
Standby process is more environmentally friendly, the utilization rate of III B element is higher, meanwhile, molecular sieve of the present invention have excellent activity, hydrothermal stability and
Preventing from heavy metal pollution performance.
Specific embodiment
Illustrate the present invention with embodiment further below, but the present invention is not limited in these examples.
(1) analysis test method used in embodiment.
1. sodium oxide molybdena, rare earth oxide, yttria levels: being analyzed using X-fluorescence method.
2. the crystallinity of molecular sieve, lattice constant: being analyzed using X-ray diffraction method.
3. the determination of activity of catalyst: being carried out in the CSA-B type catalyst evaluation device of Huayang company production.Catalyst
In advance under 800 DEG C, 100% water vapor conditions after aging 4h or 17h, huge port light diesel fuel is used to carry out determination of activity for raw material,
460 DEG C of reaction temperature, reaction time 70s, catalyst loading 5.0g, oil ratio 3.2.
(2) raw materials used specification in embodiment
1.NaY molecular sieve, kaolin (igloss 18.6%), Aluminum sol (salic 21.2 heavy %), rare earth chloride
(RE2O3 288.7g/L): it is industrial goods, picks up from Catalyst Factory of Lanzhou Petrochemical Company.
2. ammonium chloride, ammonium sulfate, yttrium oxide, yttrium nitrate, lanthanum nitrate: being solid, chemical reagent.
3. hydrochloric acid: concentration 36%, chemical reagent.
Embodiment 1
1000g NaY molecular sieve (butt) is added in 7L deionized water, under stirring, 350g ammonium chloride is added, uses
Hydrochloric acid adjusts and stirs 1h at 3.50,90 DEG C of slurry pH value, is filtered, washed later, gained filter cake and 250mL rare earth chloride, 2.2L
0.5h is stirred in deionized water mixing, then spray drying carries out hydrothermal calcine in roaster under 100% water vapour atmosphere,
600 DEG C of maturing temperature, calcining time 2 hours, obtain molecular sieve Z-1 of the present invention.
Embodiment 2
Other than by the molecular sieve after being spray-dried in embodiment 1 being roasted under 10% water vapour atmosphere, other
Molecular sieve Z-2 of the present invention is made with embodiment 1 in part.
Comparative example 1
According to existing patented technology, the comparison molecular sieve DZ-1 containing rare earth is made by ion-exchange process.
1000g NaY molecular sieve (butt) is added in 7L deionized water, under stirring, addition 350g ammonium chloride,
250mL rare earth chloride is adjusted with hydrochloric acid and stirs 1h at 3.50,90 DEG C of slurry pH value, is filtered, washed later, gained filter cake is roasting
It burns and carries out hydrothermal calcine in furnace under 100% water vapour atmosphere, 600 DEG C of maturing temperature, calcining time 2 hours.
Embodiment 3
1000g NaY molecular sieve (butt) is added in 10L deionized water, under stirring, 400g ammonium sulfate is added, uses
Hydrochloric acid adjusts and stirs 1h at 3.80,60 DEG C of slurry pH value, is filtered, washed later, gained filter cake and 102g yttrium nitrate, 2.2L go from
Sub- water and the mixing of 15g yttrium oxide, make NaY molecular sieve (butt): compound (in terms of yttrium oxide) weight ratio 1:0.045 of yttrium,
0.5h is stirred, then spray drying carries out hydrothermal calcine, maturing temperature 550 in roaster under 100% water vapour atmosphere
DEG C, calcining time 3 hours, obtain molecular sieve Z-3 of the present invention.
Comparative example 2
According to existing patented technology, the comparison molecular sieve DZ-2 containing yttrium is made by ion-exchange process.
1000g NaY molecular sieve (butt) is added in 10L deionized water, under stirring, addition 400g ammonium sulfate,
153g yttrium nitrate makes NaY molecular sieve (butt): compound (in terms of yttrium oxide) weight ratio 1:0.045 of yttrium is adjusted with hydrochloric acid
1h is stirred at 3.80,60 DEG C of slurry pH value, is filtered, washed later, gained filter cake is in roaster under 100% water vapour atmosphere
Progress hydrothermal calcine, 550 DEG C of maturing temperature, calcining time 3 hours.
Embodiment 4
1000g NaY molecular sieve (butt) is added in 8L deionized water, under stirring, 350g ammonium chloride is added, uses
Hydrochloric acid adjusts and stirs 1h at 5.00,80 DEG C of slurry pH value, is filtered, washed later, gained filter cake and 425g lanthanum nitrate, 3.0L go from
The mixing of sub- water, makes NaY molecular sieve (butt): compound (in terms of lanthana) the weight ratio 1:0.16 of lanthanum, stirs 1h at 80 DEG C,
Spray drying, then carries out hydrothermal calcine in roaster under 60% water vapour atmosphere, and 650 DEG C of maturing temperature, calcining time
2.5 hours, obtain molecular sieve Z-4 of the present invention.
Comparative example 3
According to existing patented technology, the comparison molecular sieve DZ-3 containing lanthanum is made by ion-exchange process.
1000g NaY molecular sieve (butt) is added in 8L deionized water, under stirring, addition 350g ammonium chloride,
425g lanthanum nitrate makes NaY molecular sieve (butt): compound (in terms of lanthana) weight ratio 1:0.16 of lanthanum is adjusted with hydrochloric acid
1h is stirred at 5.00,80 DEG C of slurry pH value, is filtered, washed later, gained filter cake is in roaster under 60% water vapour atmosphere
Progress hydrothermal calcine, 650 DEG C of maturing temperature, calcining time 2.5 hours.
Comparative example 4
According to existing patented technology, the comparison molecular sieve DZ-4 containing rare earth is made by ion-exchange process.
1000g NaY molecular sieve (butt) is added in 7L deionized water, under stirring, addition 350g ammonium chloride,
340mL rare earth chloride is adjusted with hydrochloric acid and stirs 1h at 3.50,90 DEG C of slurry pH value, is filtered, washed later, gained filter cake is roasting
It burns and carries out hydrothermal calcine in furnace under 100% water vapour atmosphere, 600 DEG C of maturing temperature, calcining time 2 hours.
Molecular sieve Z-1~Z-4 using the Examples 1 to 4 preparation and molecular sieve DZ-1 using the preparation of comparative example 1~4~
DZ-4, physico-chemical property analysis test result are listed in Table 1 below.
The property of 1 Y type molecular sieve of table
Table 1 the result shows that, with using existing patented technology comparative example 1 prepare molecular sieve DZ-1 compared with, using implementation
Molecular sieve Z-1, Z-2 prepared by example 1,2, sodium oxide content is suitable with comparison molecular sieve DZ-1, and the utilization rate of rare earth is 100%
Left and right, during system with molecular sieve for preparing is standby, rare earth free of losses, and the molecular sieve DZ-1 for using comparative example 1 to prepare, the utilization rate of rare earth
Only 78%, a large amount of rare earth does not exchange to molecular sieve up in exchange process, is lost during the filtration process with filtrate, makes
It is low at the utilization rate of rare earth, if environmental pollution can also be brought by not handling into the rare earth in filtrate.Illustrate molecular sieve of the present invention
Preparation process is more environmentally friendly, and rare earth utilization rate is higher.
Compared with the molecular sieve Z-2 prepared using embodiment 2, the molecular sieve Z-1 prepared using embodiment 1, due to filter cake
Hydrothermal calcine is carried out under 100% water vapour atmosphere, the crystallinity of molecular sieve is 4 percentage points high, and lattice constant is also slightly lower, explanation
It is roasted in the presence of having water vapour, is more advantageous to and keeps the complete of crystal structure of molecular sieve, while being conducive to structure cell receipts
Contracting.
Compared with the molecular sieve DZ-2 prepared using the comparative example 2 of existing patented technology, molecule prepared with embodiment 3 is adopted
Z-3 is sieved, yttrium utilization rate is 100% or so, free of losses in preparation process, and the molecular sieve DZ-2 for using comparative example 2 to prepare, yttrium
Utilization rate is only 44%, and the loss of yttrium is serious.Equally illustrate that molecular sieve preparation process of the present invention is more environmentally friendly, the utilization rate of yttrium is more
It is high.
Compared with the molecular sieve DZ-3 prepared using the comparative example 3 of existing patented technology, using the molecule of the preparation of embodiment 4
Z-4 is sieved, lanthanum utilization rate is 100% or so, free of losses in preparation process, and the molecular sieve DZ-3 for using comparative example 3 to prepare, lanthanum
Utilization rate is only 62%, and the loss of lanthanum is serious.Equally illustrate that molecular sieve preparation process of the present invention is more environmentally friendly, the utilization rate of lanthanum is more
It is high.
Compared with the molecular sieve DZ-4 prepared using the comparative example 4 of existing patented technology, using the molecule of the preparation of embodiment 1
Z-1 is sieved, rare earth utilization rate is 100% or so, free of losses in preparation process, and the molecular sieve DZ-4 for using comparative example 4 to prepare, though
Right content of rare earth is suitable with Z-1, but the utilization rate of rare earth is only 74% or so, and the loss of rare earth is serious.Equally illustrate the present invention
Molecular sieve preparation process is more environmentally friendly, and the utilization rate of rare earth is higher.
In order to investigate the cracking activity and hydrothermal stability of molecular sieve, the molecular sieve Z- of Examples 1 to 4 preparation is respectively adopted
1~Z-4 and using comparative example 1~4 prepare molecular sieve DZ-1~DZ-4, by the aluminium sol adhesive of 6% (in terms of aluminium oxide),
20% molecular sieve (butt meter), 74% kaolin (butt meter) and suitable deionized water are uniformly mixed, homogeneous, drying,
Roasting is crushed sieving, chooses the particle of 20~40 mesh, and after washing, being dry, it is old by 4h, 17h water vapour to test catalyst respectively
Activity after change, test result are listed in table 2.
In order to investigate the resistance to heavy metal pollution of molecular sieve, the particle of 20~40 mesh after above-mentioned washing, drying is used
Equi-volume impregnating impregnates 5000 μ g/g V (relative to catalyst granules) respectively, and the particle through pollution of vanadium is in 800 DEG C, 100%
4h is handled under the conditions of water vapour, the activity after testing pollution of vanadium catalyst 4h steam aging, test result is listed in table 2.
In table 2, the hydrothermal stability and an anti-huge sum of money of molecular sieve are characterized respectively with activity preservation rate R1 and activity preservation rate R2
Belong to pollution capacity.It defines respectively: activity preservation rate R1=17h steam aging activity/4h steam aging activity × 100%；
Activity preservation rate R2=pollution of vanadium 4h steam aging activity/4h steam aging activity × 100%
Activity, hydrothermal stability and the preventing from heavy metal performance of 2 Y type molecular sieve of table
Table 2 the result shows that, due to Z-1 system with molecular sieve for preparing it is standby during rare earth utilization rate is high, molecular sieve content of rare earth is high, with
It is compared using molecular sieve DZ-1 prepared by comparative example 1, is prepared using molecular sieve Z-1 prepared by the embodiment of the present invention 1 as active component
Catalyst, 4h, 17h activity has been respectively increased 7 and 9 percentage points, and activity preservation rate R1 improves 6 percentage points, illustrates this
Invention rare-earth-containing molecular sieve has higher activity and hydrothermal stability.Due to the standby rare earth utilization rate in the process of Z-2 system with molecular sieve for preparing
High, molecular sieve content of rare earth is high, compared with the molecular sieve DZ-1 prepared using comparative example 1, is prepared with the embodiment of the present invention 2
Molecular sieve Z-2 is the catalyst of active component preparation, and 4h, 17h activity have been respectively increased 3 and 5 percentage points, activity preservation rate
R1 improves 5 percentage points, illustrates that rare-earth-containing molecular sieve of the present invention has higher activity and hydrothermal stability.Due to Z-3 molecule
Utilization rate height, the yttrium content of molecular sieve for sieving yttrium in preparation process are high, compared with the molecular sieve DZ-2 prepared using comparative example 2,
Using the catalyst that molecular sieve Z-3 prepared by the embodiment of the present invention 3 is prepared as active component, 4h, 17h activity have been respectively increased 6
With 6 percentage points, activity preservation rate R1 improves 2 percentage points, illustrates that molecular sieve containing yttrium of the invention has higher active and water
Thermal stability.Since the utilization rate of the standby Rare Earth Lanthanum in the process of Z-4 system with molecular sieve for preparing is high, molecular sieve Rare Earth Lanthanum content is high, with use
Molecular sieve DZ-3 prepared by comparative example 3 is compared, and is urged using molecular sieve Z-4 prepared by the embodiment of the present invention 4 as prepared by active component
Agent, 4h, 17h activity have been respectively increased 4 and 3 percentage points, and activity preservation rate R1 is suitable, illustrate the present invention containing rare-earth molecular
Sifter device has higher activity and hydrothermal stability.Compared with the molecular sieve DZ-4 prepared using comparative example 4, with the embodiment of the present invention
The molecular sieve Z-1 of 1 preparation is the catalyst of active component preparation, 4h, 17h activity, activity preservation rate R1 with containing to score
Son sieve DZ-4 comparative catalyst it is suitable, but in rare-earth-containing molecular sieve preparation process of the present invention rare earth utilization rate it is higher.
2 result of table also indicates that, compared with the molecular sieve DZ-1~DZ-4 prepared using comparative example 1~4, is implemented with the present invention
Molecular sieve Z-1~Z-4 prepared by example 1~4 is the catalyst of active component preparation, and activity preservation rate R2 is above containing to score
The catalyst of son sieve illustrates that the catalyst containing molecular sieve of the present invention has preventing from heavy metal pollution performance.Wherein, and using comparative example
The molecular sieve DZ-1 of 1 preparation is compared, and is urged using molecular sieve Z-1, Z-2 prepared by the embodiment of the present invention 1,2 as prepared by active component
Agent, activity preservation rate R2 are respectively higher than the catalyst 8 and 6 percentage point of the molecular sieve DZ-1 containing comparison；With use comparative example 2
The molecular sieve DZ-2 of preparation is compared, the catalyst for preparing as active component of molecular sieve Z-3 prepared using the embodiment of the present invention 3, by
In the yttrium oxide for containing independent phase, trap heavy metals can be played the role of, activity preservation rate R2 is higher than the molecular sieve DZ- containing comparison
15 percentage points of 2 catalyst；Compared with the molecular sieve DZ-3 prepared using comparative example 3, divided with prepared by the embodiment of the present invention 4
Son sieve Z-4 is the catalyst of active component preparation, and activity preservation rate R2 is higher than catalyst 19 of the molecular sieve DZ-3 containing comparison
Percentage point.Although the molecular sieve DZ-4's prepared using comparative example 4 the and molecular sieve Z-1 for using the embodiment of the present invention 1 to prepare is dilute
Native content is suitable, but compared with the molecular sieve DZ-4 prepared using comparative example 4, the molecular sieve Z-1 prepared with the embodiment of the present invention 1
For the catalyst of active component preparation, activity preservation rate R2 is higher than 10 percentage points of catalyst of the molecular sieve DZ-4 containing comparison,
Illustrate that molecular sieve of the present invention has better preventing from heavy metal pollution performance.
Claims (10)
1. a kind of preparation method of super-stable Y molecular sieves, which is characterized in that preparation method include NaY molecular sieve is first used ammonium from
Son exchange mixes the compound containing III B element in the periodic table of elements after filtering, not washed directly to carry out spray drying and hydro-thermal
Roasting obtains modified super-stable Y molecular sieves.
2. preparation method according to claim 1, which is characterized in that preparation method includes the following steps:
(1) NaY molecular sieve and ammonium salt solution being subjected to ion exchange, water is 2~30: 1 with the molecular sieve ratio in terms of butt,
PH=2.8~6.5 5~100 DEG C of temperature, swap time 0.3~3.5 hour, are filtered, with water, containing period of element after Washing of Filter Cake
The compound mixing of III B element, not washed to be directly spray-dried in table, obtains containing III B element in the periodic table of elements
Molecular sieve；
(2) in roaster, by the resulting molecular sieve containing III B element in the periodic table of elements of step (1) in 10 weight %~100
Hydrothermal calcine is carried out under weight % water vapour atmosphere, 450~700 DEG C of maturing temperature, calcining time 0.5~4 hour, is modified
Super-stable Y molecular sieves.
3. preparation method according to claim 2, which is characterized in that after the molecular sieve Washing of Filter Cake in step (1), with oxygen
Compound meter, according to the molecular sieve in terms of butt: water: the weight ratio of the compound containing III B element in terms of oxide is 1: 2~8:
0.001~0.20 ratio mixing, stirred 0.5 hour at 5~100 DEG C of temperature or more, then be spray-dried.
4. preparation method according to claim 1 or 2, which is characterized in that the ammonium salt in step (1) is selected from ammonium sulfate, sulphur
Sour hydrogen ammonium, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, ammonium citrate, ammonium dihydrogen citrate, hydrogen citrate two
One of ammonium is a variety of.
5. preparation method according to claim 1 or 2 or 3, it is characterised in that it is dilute that III B element is selected from scandium, yttrium, group of the lanthanides
One of earth elements are a variety of.
6. preparation method according to claim 5, which is characterized in that the lanthanide rare be lanthanum rich rare earth, cerium-rich rare earth,
Pure lanthanum or pure cerium.
7. preparation method according to claim 1, which is characterized in that the compound containing III B element is selected from the halogen of III B element
Compound, nitrate, carbonate, oxide, hydroxide, rich III B element one of compound or a variety of.
8. preparation method according to claim 1, which is characterized in that in terms of oxide, in obtained super-stable Y molecular sieves
III B element content is 0.1~20 weight %, and sodium oxide content is 2~6 weight %.
9. preparation method according to claim 1, which is characterized in that when carrying out ion exchange in step (1), pH=2.8
~5.0,60~100 DEG C of temperature, swap time 0.5~2.5 hour.
10. preparation method according to claim 1, which is characterized in that after the molecular sieve Washing of Filter Cake in step (1), press
According to the molecular sieve in terms of butt: water: the weight ratio of the compound containing III B element in terms of oxide be 1: 2~4: 0.01~
0.15 ratio mixing, stirred 0.5 hour at 5~100 DEG C of temperature or more, then be spray-dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511020516.3A CN106927482B (en) | 2015-12-29 | 2015-12-29 | Preparation method of ultrastable Y-type molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511020516.3A CN106927482B (en) | 2015-12-29 | 2015-12-29 | Preparation method of ultrastable Y-type molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106927482A CN106927482A (en) | 2017-07-07 |
| CN106927482B true CN106927482B (en) | 2019-09-03 |
Family
ID=59442428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511020516.3A Active CN106927482B (en) | 2015-12-29 | 2015-12-29 | Preparation method of ultrastable Y-type molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106927482B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097288A (en) * | 2017-12-09 | 2018-06-01 | 北京惠尔三吉绿色化学科技有限公司 | A kind of method for preparing rare earth Y type molecular sieve |
| CN110498424B (en) * | 2018-05-16 | 2021-10-08 | 中国石油化工股份有限公司 | Method for modifying Y molecular sieve |
| CN114477217B (en) * | 2020-10-26 | 2024-03-29 | 中国石油化工股份有限公司 | Ultrastable Y-type molecular sieve and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031030A (en) * | 1987-06-09 | 1989-02-15 | 中国石化总公司石油化工科学研究院 | The preparation of low content of rare earth super-stable Y molecular sieves |
| CN1053808A (en) * | 1991-02-28 | 1991-08-14 | 中国石油化工总公司石油化工科学研究院 | A kind of preparation method of rare-earth Y molecular sieve |
| CN1221016A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Preparation of hydrocarbon cracking catalyst for preventing vanadium poisoning |
| CN1629258A (en) * | 2003-11-28 | 2005-06-22 | 中国石油化工股份有限公司 | Method for preparing cracking catalyst containing rare earth superstable Y-type molecular sieve |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214977C (en) * | 2002-12-13 | 2005-08-17 | 中国石油天然气股份有限公司 | Method for preparing zeolite molecular sieve with high activity and stability |
-
2015
- 2015-12-29 CN CN201511020516.3A patent/CN106927482B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031030A (en) * | 1987-06-09 | 1989-02-15 | 中国石化总公司石油化工科学研究院 | The preparation of low content of rare earth super-stable Y molecular sieves |
| CN1053808A (en) * | 1991-02-28 | 1991-08-14 | 中国石油化工总公司石油化工科学研究院 | A kind of preparation method of rare-earth Y molecular sieve |
| CN1221016A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Preparation of hydrocarbon cracking catalyst for preventing vanadium poisoning |
| CN1629258A (en) * | 2003-11-28 | 2005-06-22 | 中国石油化工股份有限公司 | Method for preparing cracking catalyst containing rare earth superstable Y-type molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106927482A (en) | 2017-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101385983B (en) | Heavy oil catalytic cracking catalyst | |
| US11111152B2 (en) | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst | |
| US11084024B2 (en) | Method for modifying molecular sieve and a catalytic cracking catalyst containing the molecular sieve | |
| CN101088613B (en) | Preparation process of REY molecular sieve | |
| CN103508467B (en) | A kind of rare-earth Y molecular sieve and preparation method thereof | |
| CN106925334A (en) | Heavy metal resistant heavy oil cracking catalyst and preparation method thereof | |
| CN106423252B (en) | Modification method of molecular sieve | |
| CN105562060A (en) | Catalytic cracking catalyst containing modified molecular sieve and preparation method thereof | |
| CN106927482B (en) | Preparation method of ultrastable Y-type molecular sieve | |
| CN106925335A (en) | Heavy metal resistant catalytic cracking catalyst and preparation method thereof | |
| CN103657711B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN105582973B (en) | A kind of catalyst for cracking heavy oil and preparation method thereof | |
| CN108262062A (en) | Heavy oil cracking catalyst for producing more isoolefins and preparation method thereof | |
| CN106927483B (en) | Preparation method of modified Y-type molecular sieve | |
| CN108452825A (en) | Magnesium-modified high silicon super-stable Y molecular sieves of one kind and preparation method thereof | |
| CN108262056A (en) | Catalytic cracking catalyst with adjustable pore volume and preparation method thereof | |
| CN105983431B (en) | Preparation method of silicon-based catalytic cracking catalyst | |
| CN105562061A (en) | Preparation method of modified molecular sieve | |
| CN103657712B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN105618110B (en) | A kind of Cracking catalyst and preparation method thereof | |
| CN102896000A (en) | Method for utilizing residues of catalyst production | |
| CN108201898A (en) | Method for modifying Y-type molecular sieve | |
| CN103657701B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN106890675A (en) | Preparation method of rare earth-containing catalytic cracking catalyst | |
| CN106179457A (en) | A kind of catalytic cracking catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |