CN104870368B - Use UZM-43, the hydroconversion process of a kind of EUO-NES-NON zeolite - Google Patents
Use UZM-43, the hydroconversion process of a kind of EUO-NES-NON zeolite Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 241001182492 Nes Species 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000005804 alkylation reaction Methods 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001412 amines Chemical group 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 238000009432 framing Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001884 aluminium oxide Inorganic materials 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052904 quartz Inorganic materials 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- 238000006900 dealkylation reaction Methods 0.000 claims description 2
- 230000000447 dimerizing Effects 0.000 claims description 2
- 238000007323 disproportionation reaction Methods 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006384 oligomerization reaction Methods 0.000 claims description 2
- 238000010555 transalkylation reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 6
- 201000002372 amelogenesis imperfecta type 1G Diseases 0.000 abstract 1
- 230000003197 catalytic Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 210000002356 Skeleton Anatomy 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000408939 Atalopedes campestris Species 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing Effects 0.000 description 4
- IYJYQHRNMMNLRH-UHFFFAOYSA-N Sodium aluminate Chemical compound [Na+].O=[Al-]=O IYJYQHRNMMNLRH-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- 229940113083 morpholine Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M Aluminium hydroxide oxide Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- -1 Bicyclo-[2.2.2] octane cation Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K Gallium(III) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N Silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N Trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- JJAOPSWGOJCRIY-UHFFFAOYSA-N [O-2].[Al+3].[N+](=O)(O)[O-].[O-2].[O-2].[Al+3] Chemical compound [O-2].[Al+3].[N+](=O)(O)[O-].[O-2].[O-2].[Al+3] JJAOPSWGOJCRIY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- XHODMTAOVMFHQJ-UHFFFAOYSA-N aluminum;propan-2-ol Chemical compound [Al].CC(C)O XHODMTAOVMFHQJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- LPCWKMYWISGVSK-UHFFFAOYSA-N bicyclo[3.2.1]octane Chemical compound C1C2CCC1CCC2 LPCWKMYWISGVSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001808 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011031 topaz Substances 0.000 description 1
- 229910052853 topaz Inorganic materials 0.000 description 1
- FCGQIZKUTMUWDC-UHFFFAOYSA-M trimethyl(propyl)azanium;bromide Chemical compound [Br-].CCC[N+](C)(C)C FCGQIZKUTMUWDC-UHFFFAOYSA-M 0.000 description 1
Abstract
Synthesize the new family crystalline aluminosilicate zeolitic of referred to as UZM 43.These zeolites are similar in itself previously known ERS 10, SSZ 47 and RUB 35 zeolite, but feature is unique X-ray diffraction pattern and composition and has the catalytic performance for carrying out various hydroconversion process.The catalyst being made up of these zeolites is in hydrocarbon conversion reaction.
Description
The priority request of national applications in early days
This application claims that the U. S. application No.13/718,003's that December in 2012 submits on the 18th is preferential
Power.
Background of invention
The present invention relates to zeolite UZM-43, prepare its method and as catalyst in hydrocarbon conversion side
Purposes in method.This zeolite is represented by following empirical formula:
Wherein M represents sodium or sodium and the combination of potassium exchangeable cations, and " m " is M:(Al+E) mol ratio
And be 0.05-5, R1 be single electric charge oxypropyl trimethyl ammonium cation, " r1 " is R:(Al+E) mol ratio and
Having the value of 0.25-8.0, R2 is amine, and " r2 " is R:(Al+E) mol ratio and there is the value of 0.0-5,
E is the element of the group selecting free gallium, ferrum, boron and mixture composition thereof, and " x " is the molar fraction of E
And there is the value of 0-1.0, and " y " is Si:(Al+E) mol ratio and for more than 5 to 40, and " z " is
O:(Al+E) mol ratio and there is the value determined by below equation: z=(m+r1+r2+3+4 ● y)/2.Boiling
Stone UZM-43 has the symbiosis of skeleton EUO-NES-NON.It can be as unmodified zeolite
UZM-43 or UZM-43 modified zeolite is present in catalyst.The catalyst comprising UZM-43 can
One in taking several forms, including the most spherical oil droplet catalyst or extrusion catalyst.
Zeolite is micropore and by sharing AlO2And SiO2The crystalline aluminosilicate group that tetrahedral dihedral becomes
Compound.Naturally occur with synthetically prepared a large amount of zeolites in various commercial runs.Synthetic zeolite makes
With suitable Si, Al source and structure directing agent such as alkali metal, alkaline-earth metal, amine or organic ammonium positive from
Son is prepared by hydrothermal solution synthesis.Structure directing agent occupy in the hole of zeolite and specific to ultimately form
Structure is taken the main responsibility.These species balance the skeleton electric charge relevant with aluminum and also act as space and fill out
Material.Zeolite is characterized by the perforate of uniform-dimension, has significant ion-exchange capacity and energy
The permanent zeolite of any composition of inconspicuous displacement during enough reversibly desorbing is scattered in whole crystals space
The absorption phase of the atom of crystal structure.Zeolite can be used as the catalyst of hydrocarbon conversion reaction, and described reaction exists
Carry out on inner surface on outer surface and in hole.
Three kinds of framework types EUO, NON and NES be closely-related and can by shown below along
Identical double-layer structure unit LBU A and LBU B that a ' and b ' direction of principal axis extends are constituted.LBU A by
Two dimensions connect produce the TO of the silicate plate with 12 ring openings4Tetrahedron forms.
LBU B is by TO4Tetrahedral linear chain forms.For producing the three-dimensional of EUO, NON and NES
Two class layers are stacked on c ' direction of principal axis by framing structure with characteristic order.
More than diagram display is such as perpendicular to the layered structure unit of (001) finding EUO-NES-NON race.
A () layer A is made up of [TO4] tetrahedron being interconnected and form 12 rings and (b) layer B is by being parallel to what a ' advanced
[TO4] tetrahedral rod composition.
More than diagram display framing structure representative and be such as perpendicular to (100) finding (a) NON,
The stacking order of (b) EUO and (c) NES.
For NON, only LBU A layer be stacking a).Stacking order is AA ' AA ', the most often
Every an A layer displacement 1/2a ' and be appointed as A '.Although each layer comprises 12 rings, it is thus achieved that 1/2a ' is single
The NON skeleton of alternately displacement and the generation of unit is close phase.It is actually not zeolite, but
Clathrasil because it comprise the hole of no more than 6 rings up to cage (being appointed as nns by J.V.Smith1).
EUO framework types with b) by being inserted between AA ' bilayer by B layer, thus can be stacked
Sequentially AA ' BAA ' B and formed.Gained skeleton comprises the one of the side pocket having in the truncate nns cage of entrance
Tie up 10 ring passages.
NES framework types can be with c) by replacing A and B layer to obtain stacking order
AB ' A ' BAB ' A ' B and formed, wherein A ' and B ' displacement 1/2a '.Gained skeleton comprises and is perpendicular to b '
The two dimension 10 ring passage of axle.
Disclose several relevant molecular sieve, but exist bright between those molecular sieves and molecular sieve of the present invention
Aobvious difference.At US 6, in 123,914, disclose the symbiosis of EU-1 and EUO-NES type molecular sieve,
It is for removing amorphous B and aluminum by the process of use sodium hydroxide gentleness from passage.This
The bright silica/alumina material relating to not comprising boron.
US 7,459,073 discloses to use has ring and the template (N-cyclopenta-1,4-diaza for rigidity
Bicyclo-[2.2.2] octane cation (N-cyclopenyl-1,4-diaabicyclo [2.2.2] octane cation))
Preparation molecular sieve SSZ-47B, its produce costly and can produce have more more than other material
The zeolite of EUO feature.
US 5,910,299 discloses use template such as 6-nitrogen spiral shell-[5,5]-hendecane hydroxide to be prepared
ERS-10 zeolite.Advocate that it has the Si/Al from 50 to pure silicon dioxide2Ratio.The present invention with than
The Si/Al that ERS-10 is lower2Than preparation.
The new material comprising EUO-NES-NON skeleton symbiosis being prepared in hydrocarbon method.
Summary of the invention
As discussed, the present invention relates to comprise the referred to as UZM-43 of EUO-NES-NON skeleton symbiosis
New aluminosilicate zeolites.Therefore, one embodiment of the invention is microporous crystalline zeolite, and it has
At least AlO2And SiO2The three-dimensional framework of tetrahedron element and by synthesis state and in terms of anhydrous by following warp
The experience composition that the formula of testing represents:
Wherein M represents sodium or sodium and the combination of potassium exchangeable cations, and " m " is M:(Al+E) mol ratio
And be 0.05-5, R1 be single electric charge oxypropyl trimethyl ammonium cation, " r1 " is R:(Al+E) mol ratio and
Having the value of 0.25-8.0, R2 is amine, and " r2 " is R:(Al+E) mol ratio and there is the value of 0.0-5,
E is the element of the group selecting free gallium, ferrum, boron and mixture composition thereof, and " x " is the molar fraction of E
And there is the value of 0-1.0, and " y " is Si:(Al+E) mol ratio and for more than 5 to 40, " z " is O:(Al+E)
Mol ratio and there is the value determined by below equation:
Z=(m+r1+r2+3+4 ● y)/2
And be characterised by it to have at least there is d-spacing described in Table A and the X-ray diffraction pattern of intensity.
Table A
After calcining, it was observed that X-ray diffraction pattern shown in table B.
Table B
Another aspect of the present invention is by using oxypropyl trimethyl ammonium cation (SACHEM) or propyl group
Trimethyl ammonium cation and amine prepare the method for this material.Prior art SSZ-47 material is by using
N, N-dimethyl-3-nitrogen bicyclo-[4.2.1] nonane cation or N, N-dimethyl-3-nitrogen bicyclo-[3.2.1] octane
Prepared by cation, this is more expensive and generation has EUO more more than the material prepared by the present invention
The material of feature.Prepared by the ERS-10 template 6-nitrogen spiral shell of another costliness-[5,5]-hendecane hydroxide
And preparation has higher Si/Al than UZM-432The zeolitic material of ratio.
Yet another embodiment of the invention is to use the hydroconversion process of above-mentioned zeolite.The method includes making hydrocarbon
The hydrocarbon products obtaining converting is contacted at conversion conditions with zeolite.Hydroconversion process includes that alkane splits
Change, aromatic hydrocarbons convert as xylene isomerization, toluene disproportionation, open loop and cracking with removing benzene azeotropic thing and
By aromatic hydrocarbons alkylation of paraffines.
Accompanying drawing is sketched
Fig. 1 shows as being perpendicular to the layered structure unit of EUO-NES-NON race shown in (001).
Fig. 2 show framing structure representative and be such as perpendicular to (a) NON, (b) EUO shown in (100) and
The stacking order of (c) NES.
Detailed Description Of The Invention
Applicant is prepared for topological structure matching EUO-NES-NON skeleton and is similar to as by the
International Zeolite Association Structure Commission is maintained at
The Atlas of Zeolite Framework of http://topaz.ethz.ch/IZA-SC/StdAtlas.htm
The aluminosilicate zeolites of RUB-35, SSZ-47 and ERS-10 type zeolite described in Types.These are new
Zeolite is referred to as UZM-43.As illustrated in detail, UZM-43 is it with the difference of known zeolites
Big measure feature.
As illustrated in detail in embodiment, UZM-43 material is thermally-stabilised the temperature of at least 600 DEG C,
In another embodiment, the temperature at least 800 DEG C is thermally-stabilised.The most as in the embodiment shown, UZM-43
It is the micro pore volume more than 60% that material can have the percent as total pore volume.
Prepared by the reactant mixture formed that UZM material is represented by the mol ratio having according to oxide:
aM2O:bR2/pO:1-cAl2O3:cE2O3:dSiO2:eH2O
Wherein " a " has the value of 0.05-5.0, and " b " has the value of 1.5-40, and " c " has the value of 0-1.0, " d "
Having the value of 4-40, " e " has the value of 25-4000.The source of M select free halogen, nitrate,
Acetate, hydroxide, sulfate and the group of mixture composition thereof.
Source choosing free alkali borate, boric acid, precipitation alkali formula Gallium trihydroxide., gallium sulfate, the sulfur of E
Acid ferrum, iron chloride and the group of mixture composition thereof.Aluminum source select free aluminum isopropylate., aluminium secondary butylate,
Precipitated alumina, Al (OH)3, aluminum metal and aluminium salt composition group.The most positive silicic acid four of silicon source choosing
Ethyl ester, fumed silica, cabosil and the group of precipitated silica composition.Reactant mixture is made to exist
React the 1 day time to 3 weeks at a temperature of 150-185 DEG C.Reactant mixture is preferably made to exist
React the 1 day time to 3 weeks at a temperature of 165-175 DEG C.R1 is single electric charge oxypropyl trimethyl ammonium
Cation, " r1 " is R:(Al+E) mol ratio and there is the value of 0.25-8.0, and R2 is amine, r2 is
Morpholine.The method can farther include to add in reactant mixture UZM-43 crystal seed.
Embodiment 1
Aluminosilicate reaction gel by first by 48.92g liquid sodium aluminate (LSA) (46.55% solution),
225.23g oxypropyl trimethyl ammonium hydroxide (20%SACHEM), 36.11g morpholine (Aldrich) and
865.38g water mix, simultaneously strong stirring and prepare.After being thoroughly mixed, add 224.36g
Ultrasil VN SP 89%.After interpolation completes, by gained mixture homogenization 1 hour, transfer
To 2-L Parr rustless steel agitated autoclave.By mixture at 175 DEG C along with stirring with 250RPM
Mix and crystallize 160 hours.Solid product is recovered by centrifugation, is washed with deionized and at 95 DEG C
Lower dry.Product is defined as UZM-43 by XRD.The representativeness observed about this product is spread out
Ray is shown in table 1.Product composition is determined by elementary analysis and to be made up of following mol ratio:
Si/Al=13.76, Na/Al=0.23.By a part of material by being warming up to 600 DEG C 2 hours, exist thereafter
Air stops 6 hours and calcines.BET surface area is 176m2/ g and micro pore volume are 0.07cc/g.
Scanning electron microscope (SEM) display has the crystal of circle (botryoidalis) shape less than 100nm.
Chemical analysis is as follows: 3.06%Al, 42.9%Si, 0.99%Na, N/Al=0.78, Na/Al=0.38,
Si/Al2=27.About in the diffracted ray such as table 1 below that UZM-43 observes.
Table 1
The representative diffracted ray observed about calcine UZM-43 is shown in table 2.
Table 2
Embodiment 2
Aluminosilicate reaction gel by first by 48.92g liquid sodium aluminate (LSA) (46.55% solution),
225.23g oxypropyl trimethyl ammonium hydroxide (20%SACHEM), 36.11g morpholine (Aldrich) and
865.38g water mix, simultaneously strong stirring and prepare.After being thoroughly mixed, add 224.36g
Ultrasil VN SP 89%.After interpolation completes, by gained mixture homogenization 1 hour, transfer
To 2-L Parr rustless steel agitated autoclave.By mixture at 175 DEG C along with stirring with 350RPM
Mix and crystallize 160 hours.Solid product is recovered by centrifugation, is washed with deionized and at 95 DEG C
Lower dry.Product is defined as UZM-43 by XRD.The representativeness observed about this product is spread out
Ray is shown in table 3.Product composition is determined by elementary analysis and to be made up of following mol ratio:
Si/Al=13.5, Na/Al=0.38 and N/Al=0.78.By a part of material by being warming up to 600 DEG C 2
Hour, stop 6 hours the most in atmosphere and calcine.BET surface area is 192m2/ g and porous body
Amass as 0.07cc/g.It is round-shaped that scanning electron microscope (SEM) display has less than 100nm
Crystal.
Table 3
Embodiment 3
Aluminosilicate reaction gel by first by 36.61g liquid sodium aluminate (LSA) (46.55% solution),
24.3g sodium hydroxide (50% solution) and 749.05g water mixing, simultaneously strong stirring and prepare.Thorough
After end mixing, add 421.53g propyltrimethylammonium bromide (25%SACHEM), be subsequently adding
167.99g Ultrasil VN SP 89%.After interpolation completes, by gained reactant mixture homogenizing 1
Hour, it is transferred in 2-L Parr rustless steel agitated autoclave.By mixture at 175 DEG C along with
350RPM stirs and crystallizes 132 hours.Solid product is recovered by centrifugation, is washed with deionized water
Wash and be dried at 95 DEG C.Product is defined as UZM-43 by XRD.Observe about this product
Representative diffracted ray be shown in table 4.Product composition is determined by following mol ratio by elementary analysis
Composition: Si/Al=13.05, Na/Al=0.34.By a part of material by being warming up to 600 DEG C 2 hours,
Stop 6 hours the most in atmosphere and calcine.BET surface area is 292m2/ g and micro pore volume are
0.101cc/g.Scanning electron microscope (SEM) display has the round-shaped crystal less than 100nm.
Table 4
The representative diffracted ray observed about calcine UZM-43 is shown in table 5.
Table 5
By according to embodiment 1 with 2-in-1 become UZM-43 be configured to comprise 70%UZM-43 and 30%
The catalyst of aluminium oxide.In prepared by catalyst, first by 0.17g HNO3Every gram of Catapal B
Aluminium oxide is by Catapal B aluminium oxide nitric acid peptization.Then the aluminium oxide of peptization is added in mortar,
Mix, until forming the group with the quality being suitable to extrusion simultaneously.Then extrude to be formed by this group
1/16 " diameter cylinders, is dried it whole night at 100 DEG C, is then classified into the length of 3: diameter ratio.
Dry extrudate is calcined 5 hours to remove template with moving air in an oven at 600 DEG C.Then
Calcinated support is used at 75 DEG C 10 weight %NH4NO3Solution exchanges.10g is used after this
Water/g zeolite washing.NH4NO3Exchange and washing are repeated two more times.Then by extrudate at 120 DEG C
Under be dried 4 hours, then activate at 550 DEG C.
For each sample listed in table 1, it will be observed that diffraction pattern contrast with DIFFaX simulation drawing
To obtain α N and the estimation of α S transition probability, it represents EUO, NES and NON cluster tendency.
The percent of EUO, NES and NON is calculated by transition probability.It is summarized in the best fit of simulation
In table 6.
Table 6
The DIFFaX analog result of Test Drawing
Sample 1 and 2: the sample 1 of synthesis has similar diffraction pattern with 2, and can be with phase
Same DIFFaX simulation drawing coupling.They all demonstrate that the slightest cluster is inclined in NES shape region
To with slighter in EUO and NON class region cluster tendency, thus cause having and compare NES
The structure of EUO and NON that feature is little more.
Sample 3: the sample 3 of synthesis has the diffraction pattern slightly different with first two.This figure can be with mould
Intend figure matching, show that sample comprises the NON feature more little more than first two sample and less
EUO feature.
About the diffraction of prior art sample, carry out following observation.
ERS-10., in document sample, ERS-10 has diffraction pattern most similar with the present invention, but
Existence is clearly distinguished from.This figure can show the composition being similar to simulation matching, but have little more
EUO content and Si/Al2Ratio is higher than UZM-43.
Those of the diffraction pattern of SSZ-47 and sample 1,2 and 3 are different, and with comprise more NON
The structure of feature is consistent.
RUB-35 has and those the most different diffraction patterns of the sample illustrating the present invention.Its figure with
The structure with high EUO feature is consistent.Develop the error model in RUB-35, it is believed that it is not
It it is cluster.Their best fitted is and has 78%EUO type and the structure of 22%NON type feature.
The model herein reported obtains the result (82%EUO, 12%NON, 8%NES) being similar to, Er Qiebiao
Show some NES type features of existence.
Specific embodiments
Describe hereafter together with specific embodiments, it should be understood that this description is intended to illustrate and be not intended to previously
Describe and the scope of the appended claims.
One embodiment of the invention relates to hydroconversion process, and described method includes making hydrocarbon flow and catalysis
Agent contacts to obtain converted product at hydrocarbon conversion conditions, and wherein to comprise modified UZM-43 micro-for catalyst
Hole crystalline zeolite, wherein modified UZM-43 has at least AlO2And SiO2The three-dimensional of tetrahedron element
Skeleton and the experience represented by following empirical formula in terms of anhydrous form:
Mm+R1r1R2r2Al1-xExSiyOz
Wherein M represents sodium or sodium and the combination of potassium exchangeable cations, and " m " is M:(Al+E) mol ratio
And be 0.05-5, R1 be single electric charge oxypropyl trimethyl ammonium cation, " r1 " is R:(Al+E) mol ratio and
Having the value of 0.25-8.0, R2 is amine, and " r2 " is R:(Al+E) mol ratio and there is the value of 0.0-5,
E is the element of the group selecting free gallium, ferrum, boron and mixture composition thereof, and " x " is the molar fraction of E
And there is the value of 0-1.0, and " y " is Si:(Al+E) mol ratio and for more than 5 to 40, " z " is O:(Al+E)
Mol ratio and having by equation z=(m+r1+r2+3+4 ● y)/2 values determined, and be characterised by that it has
At least there is d-spacing described in Table A and the X-ray diffraction pattern of intensity:
Table A
And it is thermally-stabilised the temperature of at least 600 DEG C and have less than 420m2The BET surface area of/g.The present invention
One embodiment be by the first embodiment in this section to previous example in this section,
Any or all, wherein hydroconversion process select free alkylation, dealkylation, the transalkylation of aromatic hydrocarbons,
The isomerization of aromatic hydrocarbons, alkene isoparaffin alkylation, dimerizing olefins, olefin oligomerization, catalysis are split
Change and the group of dewaxing composition.One embodiment of the invention is to this section by the first embodiment in this section
In middle previous example one, any or all, wherein modified UZM-43 microporous crystalline zeolite
Have and comprise 33-34 weight %EUO, 24-31 weight %NES and 34-43 weight %NON
EUO-NES-NON framing structure.One embodiment of the invention is by the first embodiment in this section
To this section in previous example, any or all, wherein catalyst comprises oxygen further
Change aluminum.
Do not further describe, it is believed that those skilled in the art can use previous description, the most complete journey
Degree ground uses the present invention.Therefore, aforementioned preferred embodiment is interpreted as being merely illustrative,
And the remainder of limit publicity content never in any form.
In the preceding article, unless otherwise noted, all temperature are DEG C to describe, and all parts and percent are with weight
Gauge.
In being previously described, those skilled in the art are readily determined the principal character of the present invention, and
The various changes and modifications of the present invention can be made to make it suitable for various use without departing from its spirit and scope
Way and condition.
Claims (8)
1. hydroconversion process, it includes making hydrocarbon flow contact at hydrocarbon conversion conditions with catalyst to obtain
Converted product, wherein catalyst comprises modified UZM-43 microporous crystalline zeolite, wherein modified UZM-43
There is at least AlO2And SiO2The three-dimensional framework of tetrahedron element and in terms of anhydrous by following empirical formula table
The experience composition shown:
Mm+R1r1R2r2Al1-xExSiyOz
Wherein M represents sodium or sodium and the combination of potassium exchangeable cations, and " m " is M:(Al+E) mol ratio
And be 0.05-5, R1 be single electric charge oxypropyl trimethyl ammonium cation, " r1 " is R:(Al+E) mol ratio and
Having the value of 0.25-8.0, R2 is amine, and " r2 " is R:(Al+E) mol ratio and there is the value of 0.0-5,
E is the element of the group selecting free gallium, ferrum, boron and mixture composition thereof, and " x " is the molar fraction of E
And there is the value of 0-1.0, " y " is Si:(Al+E) mol ratio and for more than 5 less than or equal to 40, " z " is
O:(Al+E) mol ratio and there is the value determined by below equation:
Z=(m+r1+r2+3+4 ● y)/2
And it is characterised by it to have at least having d-spacing described in Table A and the X-ray diffraction pattern of intensity:
Table A
And be heat-staple the temperature of at least 600 DEG C, and have less than 420m2The BET surface area of/g.
Method the most according to claim 1, wherein hydroconversion process select free alkylation, dealkylation,
The transalkylation of aromatic hydrocarbons, the isomerization of aromatic hydrocarbons, dimerizing olefins, olefin oligomerization, catalytic cracking and dewaxing
The group of composition.
Method the most according to claim 2, wherein alkylation includes alkene isoparaffin alkylation.
Method the most according to claim 1, wherein hydroconversion process for select free xylene isomerization,
Toluene disproportionation, open loop and cracking are to remove benzene azeotropic thing and the group formed by aromatic hydrocarbons with alkylation of paraffines
Aromatic hydrocarbons convert.
Method the most according to claim 2, wherein said hydroconversion process is alkylation.
Method the most according to claim 2, wherein said hydroconversion process is catalyst cracking method.
Method the most according to claim 1, wherein said modified UZM-43 microporous crystalline zeolite has
Comprise 33-34 weight %EUO, 24-31 weight %NES and 34-43 weight %NON
EUO-NES-NON framing structure.
Method the most according to claim 1, wherein said catalyst comprises aluminium oxide further.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/718,003 | 2012-12-18 | ||
| US13/718,003 US8993821B2 (en) | 2012-12-18 | 2012-12-18 | Hydrocarbon processes using UZM-43 an EUO-NES-NON zeolite |
| PCT/US2013/072548 WO2014099325A1 (en) | 2012-12-18 | 2013-12-02 | Hydrocarbon processes using uzm-43 an euo-nes-non zeolite |
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| CN104870368A CN104870368A (en) | 2015-08-26 |
| CN104870368B true CN104870368B (en) | 2016-11-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013606A1 (en) * | 1998-12-22 | 2000-06-28 | Exxon Research And Engineering Company | Enhancing boro-aluminosilicate zeolite structures |
| CN1104284C (en) * | 1996-03-21 | 2003-04-02 | 埃尼里塞奇公司 | ERS-10 zeolite and process for its preparation |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104284C (en) * | 1996-03-21 | 2003-04-02 | 埃尼里塞奇公司 | ERS-10 zeolite and process for its preparation |
| EP1013606A1 (en) * | 1998-12-22 | 2000-06-28 | Exxon Research And Engineering Company | Enhancing boro-aluminosilicate zeolite structures |
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