CN106607071A - Preparing method for high-cracking-activity Y-shaped molecular sieve - Google Patents
Preparing method for high-cracking-activity Y-shaped molecular sieve Download PDFInfo
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- CN106607071A CN106607071A CN201510700528.4A CN201510700528A CN106607071A CN 106607071 A CN106607071 A CN 106607071A CN 201510700528 A CN201510700528 A CN 201510700528A CN 106607071 A CN106607071 A CN 106607071A
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- Prior art keywords
- molecular sieve
- silicon source
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- meter
- alcohol
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- 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 74
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000000694 effects Effects 0.000 title claims abstract description 18
- 238000005336 cracking Methods 0.000 title claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- 230000032683 aging Effects 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- 150000007530 organic bases Chemical class 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 230000005070 ripening Effects 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 claims 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000010792 warming Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- -1 carbonium ion Chemical class 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000005216 hydrothermal crystallization Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910018512 Al—OH Inorganic materials 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical group [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- ORVGYTXFUWTWDM-UHFFFAOYSA-N silicic acid;sodium Chemical compound [Na].O[Si](O)(O)O ORVGYTXFUWTWDM-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J2029/081—Increasing the silica/alumina ratio; Desalumination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A preparing method for a high-cracking-activity Y-shaped molecular sieve is characterized by comprising the steps that a NaY molecular sieve is treated through polyhydroxy alcohol, and then mixed with an organic alkali after depolymerization, a silicon source and an aluminum source are sequentially added, and then ageing treatment is conducted, wherein the weight ratio of the aluminum source calculated on the basis of Al2O3 to the NaY molecular sieve is (0.1-1):1, the weight ratio of the aluminum source calculated on the basis of Al2O3 to the silicon source calculated on the basis of SiO2 is (2-10):1; and after ageing, the mixture is transferred into a crystallization kettle to be crystallized again, and the product is recycled. By means of the method, the silicon and aluminum atomic ratio of a molecular sieve frame is effectively increased, meanwhile, the heavy oil cracking capability of the molecular sieve can be further improved, and product distribution is optimized.
Description
Technical field
The present invention relates to a kind of preparation method of high cracking activity Y type molecular sieve.
Background technology
As the important micropore catalysis material of a class, Y type molecular sieve from last century after the sixties is synthesized,
It is used widely in modern industry.Y type molecular sieve is a kind of with faujasite structure (FAU)
Aluminosilicate, its pore passage structure are uniform, and heat and hydrothermal stability are high, and acid strong, catalysis activity is high, in stone
Oil refining and the course of processing such as catalytic cracking, be hydrocracked etc. during, Y type molecular sieve is particularly important
Cracking activity constituent element.The NaY molecular sieve sodium oxide content of hydrothermal crystallization method synthesis is higher, high-temperature water enthusiasm condition
Lower Na ions can be had an effect saboteur's sieve structure, therefore the NaY molecular sieve being directly synthesized with framework aluminum
It is not directly applicable the refining process such as catalytic cracking, it usually needs by the method for ion exchange by sodium oxide
Reduced levels are eluted to, conventional ion-exchange process includes that ammonium is exchanged and rare earth ion exchanged.
According to catalytic cracking reaction mechanism, i.e. carbonium ion reaction mechanism, it is desirable to which molecular sieve has stronger B
Acid site, simultaneously because the operating condition of catalytic cracking process is more harsh, it is special to the stability of molecular sieve
It is that hydrothermal stability requirement is higher, and the raising of molecular sieve stability is also beneficial to the reservation in acid site.Therefore
The cracking activity improved by Y type molecular sieve, on the one hand can be realized by the acid site quantity of raising molecular sieve,
On the other hand also can be realized by the stability of raising molecular sieve.
The modified method of rare earth ion is both a kind of method of sodium oxide content in eluting molecular sieve, while may be used also
The stability of framing structure is improved to form stable oxygen bridge structure with O3 by rare earth ion, so as to carry
The reserving degree in high acid site, it is ensured that higher acid site quantity and preferable cracking activity.But for
For non-rare-earth type Y molecular sieve, super stabilizing process is to improve an important channel of its stability.It is wherein high
Warm water full-boiled process, Coordinative Chemistry method, gas phase and liquid phase aluminium-eliminating and silicon-replenishing method are the more super stabilizing methods of research,
During super stabilizing, framework dealumination forms hydroxyl hole, and Si-O keys substitute Al-O keys insertion hydroxyl hole,
More stable Si-O-Si bonding structures are formed, framework si-al ratio is improved, the stability of molecular sieve strengthens,
But inevitably, super stabilizing process can affect acid distribution, cause the loss at B-acid center, Jin Erying
Ring cracking activity or selectivity.Therefore super stabilizing process can not meet high stability and peracid centric quantity simultaneously
Requirement.
The content of the invention
The purpose of the present invention is for the deficiencies in the prior art, there is provided one kind can both improve framework of molecular sieve sial
Than and stability, while and molecular sieve cracking activity can be improved and improve the preparation method of product slates.
The present invention is achieved through the following technical solutions, it is characterised in that includes：Polyhydroxy-alcohol is used first
NaY molecular sieve is processed, according to 1～20：1 alcohol sieve mass ratio is incorporated in polyhydroxy-alcohol and molecular sieve mixed
A period of time is processed at a temperature of 80～200 DEG C；According to 0.1～1：1 alkali sieve mass ratio, by organic base plus
Enter in above-mentioned serosity, then order adds silicon source and silicon source and carries out ripening, described silicon source presses Al2O3Meter
Weight ratio with NaY molecular sieve is 0.1～1：1, described silicon source is with Al2O3Meter is with silicon source with SiO2The weight of meter
Amount is than being 2～10：1, the serosity is transferred in crystallizing kettle crystallization again recovery product after ageing.
In the preparation method of the present invention, described NaY molecular sieve can various conventional methods prepare
NaY molecular sieve, is not particularly limited to parameters such as silica alumina ratio, grain sizes, degree of crystallinity typically 80% with
On, lattice constant about 2.464～2.466nm.For example, US3639099, US4482530, US4576807,
Y type molecular sieve disclosed in the documents such as CN1621349A, CN1840475A is used equally to the present invention.Alcohol process
It is front first by NaY molecular sieve and water by weight 1：5～20, preferably 1:8～15 ratio mixing beating.
In the preparation method of the present invention, it is to suitably be solved to which to process NaY molecular sieve with polyhydroxy-alcohol
It is poly-, form the Si-OH and Al-OH of activity.The preferred glycerol of described polyhydroxy-alcohol, Propylene Glycol or isopropyl
Glycol.Described alcohol sieve mass ratio is 1～20：1, preferably 3～15：1.Described treatment temperature be 80～
200 DEG C, preferably 100～180 DEG C, the time is 1～10 hour, preferably 2～8 hours.
In the preparation method of the present invention, the step of described addition organic base, after preferably processed polyhydroxy-alcohol
Serosity be cooled to room temperature after add organic base.The preferred TPAOH of described organic base, tetrem
Base ammonium hydroxide or Tetramethylammonium hydroxide.Described alkali sieve mass ratio is 0.1～1：1, preferably 0.2～
0.8：1.
In the preparation method of the present invention, described silicon source preferably sulfuric acid aluminium, aluminum nitrate, sodium metaaluminate or oxidation
Aluminum.Described silicon source presses Al2O3Meter is 0.1～1 with the weight ratio of molecular sieve：1, preferably 0.2～0.8：1.
The present invention preparation method in, the preferred waterglass of described silicon source, sodium silicate, tetraethoxy-silicane, four
Methoxyl group silicon or silicon oxide, due to preparation cost and the difference of response speed, more preferably waterglass and silicic acid
Sodium.Described silicon source is with Al2O3Meter is with silicon source with SiO2The weight ratio of meter is 2～10：1, preferably 2.5～8：
1。
In the preparation method of the present invention, described ageing is preferably carried out at 50～80 DEG C.Described crystallization mistake
5～30 hours are carried out at 100～120 DEG C of Cheng Youxuan.The process of described recovery product is people in the art
Member is be familiar with, generally include the sucking filtration to product, washing, drying, and 500～800 DEG C of roastings 2～
10 hours the step of.
The present invention preparation method, based on NaY molecular sieve, by the depolymerization of polyhydroxy-alcohol, silicon source and
Addition and the inducing action of the organic base in the hydrothermal crystallization process being again carried out step by step of silicon source so that institute
Obtain Y type molecular sieve and there is higher framework si-al ratio, while with higher cracking activity, heavy oil conversion energy
Power strengthens, and product slates are reasonably optimized.
Specific embodiment
The present invention is further illustrated for the following examples, but not thereby limiting the invention.
In each embodiment and comparative example, the framework silicon-aluminum atomic ratio (Si/Al) of molecular sieve adopts solid core
Magnetic NMR methods are determined.Cracking activity is determined using fixed bed heavy oil micro anti-evaluation device.
Embodiment 1
By 20g (butt) industry NaY molecular sieve (Na2O 12.9%, degree of crystallinity 89%, framework silicon-aluminum atom
Than 2.67, Sinopec Chang Ling catalyst plant) mix with 160g water, add 40g glycerol and at 180 DEG C
Lower process 4h, decomposes molecular sieve generating unit poly-；Serosity after depolymerization is processed is cooled to room temperature, under stirring
32g TPAOH solution (mass fraction 25wt%) is added, 40 DEG C is warming up to again and by 6.4mL waterglass
Solution (SiO23.3) content 250g/L, modulus are added thereto, and add 42mL after continuing stirring certain hour
Sodium metaaluminate (Al2O3Content 190g/L), then raise temperature to 60 DEG C of ageing 2h.Serosity after ageing is turned
Move in crystallizing kettle in 120 DEG C of crystallization 15h, product is Jing filtering, washing, be dried after, the roasting at 550 DEG C
2h, that is, obtain molecular sieve of the present invention and be designated as GYC-1.XRD spectra shows which has typical Y type molecular sieve
Architectural feature.
Embodiment 2
20g (butt) industry NaY molecular sieve (ibid) is mixed with 200g water, addition 130g the third three
Alcohol simultaneously processes 8h at 120 DEG C；Serosity after depolymerization is processed is cooled to room temperature, and stirring is lower to add 20g
17mL water glass solutions are added thereto under room temperature by TPAOH solution, are added after continuing stirring certain hour
150mL aluminum sulfate (Al2O3Content 90g/L), it is warming up to 70 DEG C of ageing 2h.Serosity after ageing is shifted
Into crystallizing kettle in 100 DEG C of crystallization 20h, product Jing filter, washing, be dried after, the roasting at 650 DEG C
4h, that is, obtain molecular sieve of the present invention and be designated as GYC-2.XRD spectra shows which has typical Y type molecular sieve
Architectural feature.
Embodiment 3
20g (butt) industry NaY molecular sieve (ibid) is mixed with 100g water, addition 190g the third two
Alcohol simultaneously processes 4h at 140 DEG C；Serosity after depolymerization is processed is cooled to room temperature, and stirring is lower to add 56g
TMAOH solution (mass fraction 25wt%), is warming up to 60 DEG C again and is added thereto 25g tetraethoxy-silicanes,
84mL sodium metaaluminates, continuation is added to be aged 2h at 60 DEG C after continuing stirring a period of time.After ageing
Serosity is transferred in crystallizing kettle in 110 DEG C of crystallization 10h, product is Jing filtering, washing, be dried after, at 600 DEG C
Lower roasting 6h, that is, obtain molecular sieve of the present invention and be designated as GYC-3.XRD spectra shows which has typical Y types
The architectural feature of molecular sieve.
Embodiment 4
By 20g (butt) industry NaY molecular sieve (Na2O 13.2%, degree of crystallinity 85%, framework silicon-aluminum atom
Than 2.64, Sinopec Shandong catalyst plant) mix with 200g water, add 80g glycerol and at 170 DEG C
Lower process 6h；Serosity after depolymerization is processed is cooled to room temperature, and stirring is lower to add 44g TEAOH solution (matter
Amount fraction 25wt%), 50 DEG C are warming up to again and 10mL water glass solutions are added thereto, continue stirring one
125mL aluminum nitrate solution (Al are added after fixing time2O3Content 80g/L), it is warming up to 80 DEG C of ageing 2h.Will
Serosity after ageing is transferred in crystallizing kettle in 100 DEG C of crystallization 10h, product is Jing filtering, washing, be dried after,
The roasting 4h at 550 DEG C, that is, obtain molecular sieve of the present invention and be designated as GYC-4.XRD spectra shows which has allusion quotation
The architectural feature of the Y type molecular sieve of type.
Embodiment 5
20g (butt) industry NaY molecular sieve (with embodiment 4) is mixed with 160g water, 240g is added
Propylene Glycol simultaneously processes 2h at 150 DEG C；Serosity after depolymerization is processed is cooled to room temperature, and stirring is lower to add 40g
3g tetraethoxy-silicanes are added thereto under room temperature by TPAOH solution and 24gTEAOH solution, continue stirring one
31mL sodium metaaluminates are added after the section time, 50 DEG C of ageing 2h are warming up to.Serosity after ageing is transferred to into crystalline substance
Change in kettle in 120 DEG C of crystallization 10h, product is Jing filtering, washing, be dried after, the roasting 4h at 650 DEG C,
Obtain molecular sieve of the present invention and be designated as GYC-5.XRD spectra shows which has the knot of typical Y type molecular sieve
Structure feature.
Embodiment 6
20g (butt) industry NaY molecular sieve (with embodiment 4) is mixed with 120g water, 170g is added
Glycerol simultaneously processes 8h at 100 DEG C；Serosity after depolymerization is processed is cooled to room temperature, and stirring is lower to add 28g
TEAOH solution, is warming up to 40 DEG C again and is added thereto 19mL water glass solutions, continues one section of stirring
63mL sodium metaaluminates are added after time, 70 DEG C of ageing 2h are warming up to.Serosity after ageing is transferred to into crystallization
In 110 DEG C of crystallization 15h in kettle, product Jing filter, washing, be dried after, the roasting 3h at 600 DEG C, i.e.,
Obtain molecular sieve of the present invention and be designated as GYC-6.XRD spectra shows which has the structure of typical Y type molecular sieve
Feature.
Embodiment 7
20g (butt) industry NaY molecular sieve (with embodiment 4) is mixed with 160g water, 120g is added
Propylene Glycol simultaneously processes 10h at 130 DEG C；Serosity after depolymerization is processed is cooled to room temperature, and stirring is lower to be added
16g TMAOH solution, is warming up to 50 DEG C again and is added thereto 5.6mL water glass solutions, continues stirring
50mL aluminum nitrates are added after a period of time, 80 DEG C of ageing 2h are warming up to.Serosity after ageing is transferred to into crystalline substance
Change in kettle in 100 DEG C of crystallization 10h, product is Jing filtering, washing, be dried after, the roasting 2h at 550 DEG C,
Obtain molecular sieve of the present invention and be designated as GYC-7.XRD spectra shows which has the knot of typical Y type molecular sieve
Structure feature.
Comparative example 1
This comparative example is illustrated with embodiment 1, but difference is the silicon source contrast different with silicon source addition sequence
Journey.
Take 20g (butt) industry NaY molecular sieve (with embodiment 1) to mix with 160g water, add 40g
Glycerol simultaneously processes 4h at 180 DEG C, decomposes molecular sieve generating unit poly-；Serosity after depolymerization is processed is cold
But to room temperature, stirring is lower to add 32g TPAOH solution, is warming up to 40 DEG C again and by 42mL sodium metaaluminates
Be added thereto, continue stirring certain hour after add 6.4mL water glass solutions, then raise temperature to 60 DEG C it is old
Change 2h.Serosity after ageing is transferred in crystallizing kettle in 120 DEG C of crystallization 15h, product Jing is filtered, washing,
After drying, the roasting 2h at 550 DEG C obtains contrast molecular sieve and is designated as DB-1.XRD spectra shows which is same
Sample has the architectural feature of typical Y type molecular sieve.
Comparative example 2
This comparative example illustrated with embodiment 1, but difference be silicon source and silicon source be addition simultaneously comparison process.
Take 20g (butt) industry NaY molecular sieve (with embodiment 1) to mix with 160g water, add 40g
Glycerol simultaneously processes 4h at 180 DEG C, decomposes molecular sieve generating unit poly-；Serosity after depolymerization is processed is cold
But to room temperature, stirring is lower to add 32g TPAOH solution, is warming up to 40 DEG C again and with simultaneously stream mode while will
42mL sodium metaaluminates and 6.4mL water glass solutions are added thereto, and then raise temperature to 60 DEG C of ageing 2h.Will be old
Serosity after change is transferred in crystallizing kettle in 120 DEG C of crystallization 15h, product is Jing filtering, washing, be dried after,
The roasting 2h at 550 DEG C, that is, obtain contrast molecular sieve and be designated as DB-2.XRD spectra shows which equally has allusion quotation
The architectural feature of the Y type molecular sieve of type.
Test case
This test case illustrates the framework si-al ratio and sample of the sieve sample that above-described embodiment and comparative example are obtained
Product are Jing the heavy oil micro anti-evaluation result after burin-in process under 800 DEG C, 100% water vapor conditions 17 hours.
Exchanged the oxidation in embodiment sample GYC-1～GYC-7 and comparative sample DB-1, DB-2 using ammonium
Sodium content is washed till less than 0.3wt%, and tabletting simultaneously grinds to form 20～40 mesh granules, is steamed in 800 DEG C, 100% water
Burin-in process 17 hours evaluated on fixed bed heavy oil microreactor under the conditions of gas.Appreciation condition is
Agent oil quality compares 1.4, molecular sieve reserve 2g, and raw oil is VGO, 500 DEG C of reaction temperature, regeneration temperature
600℃。
Framework si-al ratio analytical data is shown in Table 1.Raw oil characterisitic parameter is shown in Table 2, heavy oil micro anti-evaluation result
It is shown in Table 3.
Table 1
| Sample ID | Skeleton Si/Al | Sample ID | Skeleton Si/Al | |
| GYC-1 | 2.87 | GYC-6 | 3.07 | |
| GYC-2 | 3.11 | GYC-7 | 2.84 | |
| GYC-3 | 3.18 | DB-1 | 2.72 | |
| GYC-4 | 2.98 | DB-2 | 2.69 | |
| GYC-5 | 2.82 |
Table 2
Table 3
| Sample ID | Conversion ratio/% | Slurry oil yield/% | Yield of light oil/% |
| GYC-1 | 65.18 | 13.20 | 70.09 |
| GYC-2 | 70.50 | 9.05 | 71.91 |
| GYC-3 | 68.83 | 10.46 | 71.00 |
| GYC-4 | 67.58 | 10.73 | 71.45 |
| GYC-5 | 63.27 | 15.02 | 66.07 |
| GYC-6 | 71.61 | 8.37 | 72.27 |
| GYC-7 | 63.79 | 14.20 | 66.70 |
| DB-1 | 62.81 | 15.60 | 67.47 |
| DB-2 | 63.73 | 14.57 | 68.68 |
From table 1, using the preparation method of present invention offer, in the presence of polyhydroxy-alcohol, molecular sieve
In structure, generating unit decomposes poly- phenomenon, forms the Si-OH and Al-OH of activity, using selected addition silicon source and
The guide effect of the order and organic base of silicon source and hydrothermal crystallization process again, can effectively improve molecule
The framework silicon-aluminum atomic ratio of sieve.
From table 3, Jing after 800 DEG C, 17h burin-in process, the conversion ratio of sieve sample in embodiment
63.27～71.61% are reached, between 8.37～15.02%, yield of light oil can reach slurry oil yield
66.07～72.27%.Compared with addition comparative sample DB-1～2 prepared by different silicon and aluminum source addition sequences,
In embodiment 1, the cracking activity of sample GYC-1 is higher, and heavy oil conversion performance is higher, and slurry oil yield is low, liquid
Body yield substantially increases, and product slates are optimized.
Claims (12)
1. a kind of preparation method of high cracking activity Y type molecular sieve, it is characterised in that include using polyhydroxy-alcohol
NaY molecular sieve is processed, according to 1～20：1 alcohol sieve mass ratio is incorporated in polyhydroxy-alcohol and molecular sieve mixed
A period of time is processed at a temperature of 80～200 DEG C；According to 0.1～1：1 alkali sieve mass ratio, by organic base plus
Enter in above-mentioned serosity, then order adds silicon source and silicon source and carries out ripening, described silicon source presses Al2O3Meter
Weight ratio with NaY molecular sieve is 0.1～1：1, described silicon source is with Al2O3Meter is with silicon source with SiO2The weight of meter
Amount is than being 2～10：1, the serosity is transferred in crystallizing kettle crystallization again recovery product after ageing.
2. according to the preparation method of claim 1, described polyhydroxy-alcohol selected from glycerol, Propylene Glycol or
Isopropanediol.
3., according to the preparation method of claim 1, described alcohol sieve mass ratio is 1～20：1, it is described
Treatment temperature is 80～200 DEG C, and process time is 1～10h.
4., according to the preparation method of claim 1, described alkali sieve mass ratio is 0.1～1：1, preferably
0.2～0.8:1.
5. according to the preparation method of claim 1, described organic base selected from TPAOH, four
Ethyl ammonium hydroxide or Tetramethylammonium hydroxide.
6., according to the preparation method of claim 1, described ageing, temperature are 50～80 DEG C.
7., according to the preparation method of claim 1, described silicon source is selected from aluminum sulfate, aluminum nitrate, inclined aluminum
Sour sodium or aluminium oxide.
8., according to the preparation method of claim 1, silicon source presses Al2O3Count and with the weight ratio of NaY molecular sieve be
0.1～1：1.
9., according to the preparation method of claim 8, silicon source presses Al2O3Count and with the weight ratio of NaY molecular sieve be
0.2～0.8：1.
10., according to the preparation method of claim 1, described silicon source is selected from waterglass, sodium silicate, tetrem
Epoxide silicon, tetramethoxy-silicane or silicon oxide.
11. according to claim 1 preparation method, silicon source is with Al2O3Meter is with silicon source with SiO2The weight of meter
Than for 2～10：1.
12. according to claim 11 preparation method, silicon source is with Al2O3Meter is with silicon source with SiO2The weight of meter
Than for 2.5～8：1.
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| CN107720776A (en) * | 2017-10-23 | 2018-02-23 | 中海油天津化工研究设计院有限公司 | A kind of synthetic method of no sodium FAU type molecular sieves |
| CN112058304A (en) * | 2019-11-20 | 2020-12-11 | 榆林学院 | Dual-function catalyst capable of adjusting solid acidity, preparation method and application thereof |
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| WO2009075947A1 (en) * | 2007-12-11 | 2009-06-18 | Uop Llc | Method for making high performance mixed matrix membranes |
| CN103100433A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of composite carrier material |
| EP2857096A1 (en) * | 2012-06-01 | 2015-04-08 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
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| WO2009075947A1 (en) * | 2007-12-11 | 2009-06-18 | Uop Llc | Method for making high performance mixed matrix membranes |
| CN103100433A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of composite carrier material |
| EP2857096A1 (en) * | 2012-06-01 | 2015-04-08 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
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| CN107720776A (en) * | 2017-10-23 | 2018-02-23 | 中海油天津化工研究设计院有限公司 | A kind of synthetic method of no sodium FAU type molecular sieves |
| CN107720776B (en) * | 2017-10-23 | 2020-02-18 | 中海油天津化工研究设计院有限公司 | Synthesis method of sodium-free FAU type molecular sieve |
| CN112058304A (en) * | 2019-11-20 | 2020-12-11 | 榆林学院 | Dual-function catalyst capable of adjusting solid acidity, preparation method and application thereof |
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