CN105080599B - It is layered zeolite type alkyl aromatic hydrocarbon isomerization catalyst - Google Patents
It is layered zeolite type alkyl aromatic hydrocarbon isomerization catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000010457 zeolite Substances 0.000 title claims abstract description 62
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 26
- -1 alkyl aromatic hydrocarbon Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 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 24
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 6
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 83
- 229910052739 hydrogen Inorganic materials 0.000 claims description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 229930195733 hydrocarbon Natural products 0.000 claims description 35
- 150000002430 hydrocarbons Chemical class 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 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 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 48
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 44
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 32
- 239000012690 zeolite precursor Substances 0.000 description 32
- 239000004215 Carbon black (E152) Substances 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000843 powder Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 20
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 238000009825 accumulation Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000000969 carrier Substances 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 8
- 230000001404 mediated effect Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- YYWWIAMIOQXSER-UHFFFAOYSA-M diethyl(dimethyl)azanium;bromide Chemical compound [Br-].CC[N+](C)(C)CC YYWWIAMIOQXSER-UHFFFAOYSA-M 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- KHBDINVATPZDSQ-UHFFFAOYSA-M dimethyl(dipropyl)azanium;bromide Chemical compound [Br-].CCC[N+](C)(C)CCC KHBDINVATPZDSQ-UHFFFAOYSA-M 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 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 1
- 239000000463 material Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to one kind layering zeolite type alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof, mainly solves the opening cyclic paraffins side reaction that can not ignore present in prior art, and then possible adjoint cracking issues.The present invention includes a) 30~90% SiO by weight percentage by using zeolite type alkyl aromatic hydrocarbon isomerization catalyst is layered2/Al2O3Mol ratio is 5~200 layering zeolites with MWW structures；B) 0.05~1%Pt；C) 0.001~0.1% lanthanide series；D) surplus preferably solves the problem for the technical scheme of aluminum oxide, available for C8In the isomerization industrial production of aromatic hydrocarbons.
Description
Technical field
The present invention relates to one kind layering zeolite type alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof, and C8Aromatic hydrocarbons is different
The method of structure.
Background technology
C8Aromatic hydrocarbons is mainly derived from catalytic reformate, pyrolysis gasoline, in addition, also toluene disproportionation or transalkylated product
And coal tar etc..The C in above-mentioned source8In aromatic hydrocarbons except containing to, in addition to ortho-xylene, also contain ethylbenzene.Due to ethylbenzene and diformazan
The boiling point of benzene is very close, and the processing charges height of ethylbenzene is directly separated according to highly efficient distilling or adsorbing separation, uneconomical, so
General oil company converts the ethylbenzene into dimethylbenzene or benzene using chemical reaction more.The C in above-mentioned source8Aromatic hydrocarbons composition is substantially at
Thermodynamic equilibrium state, paraxylene is in C820% is only accounted in aroamtic hydrocarbon raw material.And paraxylene is the original of synthetic fibers, polyester etc.
Material, demand is big, added value is high, therefore for through numerous benefit and social benefit, increasing yield of p-xylene is a meaning weight
Big work.
C8Aromatic hydrocarbons extracts paraxylene by separation method or uses xylene isomerization to, ortho-xylene, its raffinate
Method, the raffinate of non-equilibrium composition is converted into equilibrium composition, circulating isomery by raffinate separates, can by meta-xylene or
Between, ortho-xylene be completely converted into paraxylene or to, ortho-xylene.
When isomerization uses acidic catalyst, ethylbenzene can be disproportionated under harsher operating condition and take off alkyl
Reaction, so as to generate benzene and heavy aromatics, meanwhile, with dimethylbenzene transalkylation reaction also occurs for ethylbenzene, and this kind of reaction will influence mesh
Product to the yield of, ortho-xylene.
When isomerization uses bifunctional catalyst, ethylbenzene is in C8Dimethylbenzene, ethylbenzene conversion can be converted into the presence of cycloalkane
For dimethylbenzene selectivity up to more than 50%.
Ethylbenzene isomerization needs VIII noble metal to exist into dimethylbenzene, is traditionally inclined to use modenite, ZSM series
Zeolite.As US4482773 selects ZSM-5 zeolite.EP458378 describes a kind of C8Arene isomerization catalyst, contain platinum activity
Component, and a kind of H type modenites containing 2~3% alkali metal, and bonded from hibbsite or gama-alumina
Agent.Modenite is converted into H type modenites by the catalyst by ion exchange, is then mixed with binding agent, or first will
Modenite mixes with binding agent, is then molded, and ion exchange, provides H- modenites, is finally impregnated with platinum, then is calcined also
It is former.
US6150292A(Catalyst for isomerizing aromatic C8Cuts) describe one kind and be used for C8Virtue
The isomerization catalyst of hydrocarbon-fraction, from the modenite between silica alumina ratio 5-10 and a kind of binding agent, taken containing at least one
Platinum and palladium from periodic table group VIII element, at the same in catalyst containing at least one gallium for being derived from periodic table III-th family,
The preferred indium of indium, thallium, and at least one preferred tin of germanium, tin, lead for being derived from periodic table Group IV.But the pair that its presence can not be ignored is anti-
Should.
The content of the invention
One of technical problems to be solved by the invention are the opening cyclic paraffins pairs that can not ignore present in prior art
Reaction, and then possible adjoint cracking issues, there is provided a kind of new catalyst for Alleyl aromatics isomerizating.The catalysis
Agent is used for C8When aromatics isomerization reacts, concentration of the paraxylene in dimethylbenzene reaches or close to thermodynamical equilibrium in product,
Paraxylene high income, while ethylbenzene can be converted largely.
The two of the technical problems to be solved by the invention are the preparation methods of one of above-mentioned technical problem catalyst.
The three of the technical problems to be solved by the invention are the C using one of the above-mentioned technical problem catalyst8Aromatic hydrocarbons
Isomerization method.
To solve one of above-mentioned technical problem, technical scheme is as follows：It is layered zeolite type Alleyl aromatics isomerizating
Catalyst, by weight percentage including following components：
A) 30~90%SiO2/Al2O3Mole be 5~200 the layering zeolite with MWW structures；
B) 0.05~1%Pt；
C) 0.001~0.1% lanthanide series；Wherein described lanthanide series preferably is selected from La, Ce, Pr, Nd and Yb extremely
Few one kind；Especially while during including La and Pr, La and Pr have synergy；Most preferably La and Pr mol ratios 0.2~5；
D) surplus is aluminum oxide.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of layering zeolite type alkyl aromatic hydrocarbon isomerization catalyst described in case, comprises the following steps：
(1) mixture containing silicon source, silicon source, template, alkali metal ion and water that pH first is 7.5~14 80~
200 DEG C of crystallization obtain precursor carrier in 5~400 hours；
The mixture is formed with molar ratio computing is：Alkali metal ion/SiO2=0.01~4；Template/SiO2=0.01
~4；
The template has below general formula：
Wherein R1For-(CH2)mCH3；R2For-(CH2)nCH3；R3For-(CH2)lCH3；R4For-(CH2)kCH3；
M, n and l are 0~3 integer, and m >=n, and m>l,m>k；Y is selected from halogen or OH；Alkali metal be derived from Li, Na, K,
At least one of Ru, Cs；
(2) aluminum oxide is binding agent, and shaping obtains precursor carrier 2；
(3) roasting obtains carrier；Sintering temperature is preferably 300~600；Roasting time is preferably 3~6 hours；
(4) carrier is mixed with the soluble compound solution of Pt and lanthanide series, obtains catalyst precarsor I；
(5) reducing catalyst precursor I obtains described catalyst.
In above-mentioned technical proposal, silicon source preferably be selected from silester, amorphous silica, Ludox, silica gel, diatomite and
At least one of waterglass；Silicon source preferably be selected from aluminium hydroxide, aluminium isopropoxide, aluminium secondary butylate, sodium aluminate, aluminum sulfate, aluminum nitrate,
At least one of aluminium chloride and aluminum oxide.
In above-mentioned technical proposal, it is crystal seed that the mixture of step (1), which preferably also contains with MWW structures layered zeolite,；Its
SiO in the mixture is preferably accounted for by weight percentage2The 0.02~40% of weight.
In above-mentioned technical proposal, the silica alumina ratio with MWW structural stratification zeolites is preferably 20~100.
In above-mentioned technical proposal, the reduction of step (5) can be reduced using reducing agent well known in the art.Such as adopt
Use hydrogen reducing.When being reduced using hydrogen as reducing agent, it is preferred to use the hydrogen nitrogen mixture of the hydrogen containing 5w% is also
Original, reduction temperature are preferably 300~550 DEG C；Recovery time is preferably 1~8 hour.
To solve the three of above-mentioned technical problem, technical scheme is as follows：C8The isomerization method of aromatic hydrocarbons, above-mentioned
In the presence of catalyst described in the technical scheme of one of technical problem, with C8Aromatic hydrocarbons obtains different for raw material generation isomerization reaction
Structure product.
In above-mentioned technical proposal, reaction temperature is preferably 250~600 DEG C, more preferably 350~510 DEG C.
In above-mentioned technical proposal, the pressure of reaction is preferably 0.06MPa~10MPa, more preferably 0.3MPa in terms of gauge pressure
~3MPa.
In above-mentioned technical proposal, the weight space velocity of the raw material is preferably 0.6~210 hour-1, more preferably 3~110 is small
When-1。
In above-mentioned technical proposal, in order to extend the life-span of catalyst, carry out isomerization reaction preferably is left in hydrogen, now
Mol ratio (the H of hydrogen and raw material2/ HC) it is preferably 0.6~15；More preferably 2~7.
In above-mentioned technical proposal, described C8Cut aromatic hydrocarbons preferably comprises dimethylbenzene (o-, m-, contraposition), further preferably
Contain dimethylbenzene (o-, m-, contraposition) and ethylbenzene.
The performance of catalyst is calculated as follows method evaluation：
The catalyst of the present invention is used for C8During the isomerization of aromatic hydrocarbons, the ortho-xylene balance degree of approach is up to 98.6%, ethylbenzene
For high conversion rate up to 68.8%, the selectivity that ethylbenzene is converted into dimethylbenzene is up to 66.3%, achieves preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Figure of description
Fig. 1 is the X-ray diffraction spectrum with MWW structural stratification zeolites of synthesis.
XRD spectrums have one more to change peak at 7 °~11 ° in Fig. 1, show to prepare boiling of the MWW zeolites for unordered accumulation hierarchy
Stone.
Embodiment
【Embodiment 1】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 17 grams of concentration be 20w% (with Al2O3Meter) sulphur
Sour aluminum water solution, 2 grams of MWW zeolite seed crystals, 20 grams of dimethyl diethyl ammonium bromide mix with 30 grams of water, and are 10w% with concentration
The NaOH aqueous solution pH is transferred to 10, continue stirring 30 minutes, move into stainless steel cauldron, in 150 DEG C of crystallization 72 hours, mistake
Filter, washing, the XRD powder diffraction spectrums of dried product exhibited are shown in accompanying drawing 1, and it has one more to change peak at 7 °~11 °, shows system of the present invention
Standby product is the Hydrogen stratiform MWW zeolite precursors 1 of unordered accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 10w%,
Ammonium type MWW zeolites are obtained within 3 hours in 60 DEG C of ion exchanges；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 3 hours through 550 DEG C of roastings；
(5) weigh 60 grams of Hydrogen MWW zeolite powders to mix with 25.7 grams of alumina powders, by 100:60 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) 49.85 grams of catalyst carriers are weighed to mix containing Pt0.13 grams, containing La0.02 grams of chloroplatinic acid lanthanum nitrate with 50 grams
The aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(9) described urge is produced within 6 hours in 450 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Embodiment 2】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 17 grams of concentration be 20w% (with Al2O3Meter) sulphur
Sour aluminum water solution, 2 grams of MWW zeolite seed crystals, 20 grams of dimethyl diethyl ammonium bromide mix with 30 grams of water, and are 10w% with concentration
The NaOH aqueous solution pH is transferred to 10, continue stirring 30 minutes, move into stainless steel cauldron, in 150 DEG C of crystallization 72 hours, mistake
Filter, washing, the XRD powder diffraction spectrums of dried product exhibited also have one more to change peak, show this hair as accompanying drawing 1 at 7 °~11 °
The product of bright preparation is the Hydrogen stratiform MWW zeolite precursors 1 of unordered accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 10w%,
Ammonium type MWW zeolites are obtained within 3 hours in 60 DEG C of ion exchanges；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 3 hours through 550 DEG C of roastings；
(5) weigh 60 grams of Hydrogen MWW zeolite powders to mix with 25.7 grams of alumina powders, by 100:60 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) 49.85 grams of catalyst carriers are weighed to mix containing Pt0.13 grams, containing Pr0.02 grams of chloroplatinic acid praseodymium nitrate with 50 grams
The aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(9) described urge is produced within 6 hours in 450 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Embodiment 3】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 17 grams of concentration be 20w% (with Al2O3Meter) sulphur
Sour aluminum water solution, 2 grams of MWW zeolite seed crystals, 20 grams of dimethyl diethyl ammonium bromide mix with 30 grams of water, and are 10w% with concentration
The NaOH aqueous solution pH is transferred to 10, continue stirring 30 minutes, move into stainless steel cauldron, in 150 DEG C of crystallization 72 hours, mistake
Filter, washing, the XRD powder diffraction spectrums of dried product exhibited also have one more to change peak, show this hair as accompanying drawing 1 at 7 °~11 °
The product of bright preparation is the Hydrogen stratiform MWW zeolite precursors 1 of unordered accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 10w%,
Ammonium type MWW zeolites are obtained within 3 hours in 60 DEG C of ion exchanges；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 3 hours through 550 DEG C of roastings；
(5) weigh 60 grams of Hydrogen MWW zeolite powders to mix with 25.7 grams of alumina powders, by 100:60 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) 49.85 grams of catalyst carriers are weighed to mix containing Pt0.13 grams, containing Nd0.02 grams of chloroplatinic acid neodymium nitrate with 50 grams
The aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(9) described urge is produced within 6 hours in 450 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Embodiment 4】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 17 grams of concentration be 20w% (with Al2O3Meter) sulphur
Sour aluminum water solution, 2 grams of MWW zeolite seed crystals, 20 grams of dimethyl diethyl ammonium bromide mix with 30 grams of water, and are 10w% with concentration
The NaOH aqueous solution pH is transferred to 10, continue stirring 30 minutes, move into stainless steel cauldron, in 150 DEG C of crystallization 72 hours, mistake
Filter, washing, the XRD powder diffraction spectrums of dried product exhibited also have one more to change peak, show this hair as accompanying drawing 1 at 7 °~11 °
The product of bright preparation is the Hydrogen stratiform MWW zeolite precursors 1 of unordered accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 10w%,
Ammonium type MWW zeolites are obtained within 3 hours in 60 DEG C of ion exchanges；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 3 hours through 550 DEG C of roastings；
(5) weigh 60 grams of Hydrogen MWW zeolite powders to mix with 25.7 grams of alumina powders, by 100:60 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) 49.85 grams of catalyst carriers are weighed to mix containing Pt0.13 grams, containing Yb0.02 grams of chloroplatinic acid ytterbium nitrate with 50 grams
The aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(9) described urge is produced within 6 hours in 450 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Embodiment 5】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 17 grams of concentration be 20w% (with Al2O3Meter) sulphur
Sour aluminum water solution, 2 grams of MWW zeolite seed crystals, 20 grams of dimethyl diethyl ammonium bromide mix with 30 grams of water, and are 10w% with concentration
The NaOH aqueous solution pH is transferred to 10, continue stirring 30 minutes, move into stainless steel cauldron, in 150 DEG C of crystallization 72 hours, mistake
Filter, washing, the XRD powder diffraction spectrums of dried product exhibited also have one more to change peak, show this hair as accompanying drawing 1 at 7 °~11 °
The product of bright preparation is the Hydrogen stratiform MWW zeolite precursors 1 of unordered accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 10w%,
Ammonium type MWW zeolites are obtained within 3 hours in 60 DEG C of ion exchanges；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 3 hours through 550 DEG C of roastings；
(5) weigh 60 grams of Hydrogen MWW zeolite powders to mix with 25.7 grams of alumina powders, by 100:60 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) weigh 49.85 grams of catalyst carriers with 50 grams containing Pt0.13 grams, containing La0.0135 grams, containing Pr0.0065 grams
Chloroplatinic acid lanthanum nitrate praseodymium nitrate mixed aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(9) described urge is produced within 6 hours in 450 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Embodiment 6】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 204 grams of concentration be 20w% (with Al2O3Meter)
Aluminum sulfate aqueous solution, 0.025 gram of MWW zeolite seed crystals, 20 grams of dimethyl diethyl ammonium bromide mix with 30 grams of water, and are with concentration
PH is transferred to 10 by the 10w% NaOH aqueous solution, continues stirring 30 minutes, is moved into stainless steel cauldron, small in 150 DEG C of crystallization 72
When, filtering, washing, the XRD powder diffraction spectrums of dried product exhibited also have one more to change peak, table as accompanying drawing 1 at 7 °~11 °
Product prepared by the bright present invention is the Hydrogen stratiform MWW zeolite precursors 1 of unordered accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 20w%,
Ammonium type MWW zeolites are obtained within 3 hours in 90 DEG C of ion exchanges；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 6 hours through 500 DEG C of roastings；
(5) weigh 25.7 grams of Hydrogen MWW zeolite powders to mix with 60 grams of alumina powders, by 100:60 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) weigh 49.85 grams of catalyst carriers with 50 grams containing Pt0.13 grams, containing La0.0035 grams, containing Pr0.0165 grams
Chloroplatinic acid lanthanum nitrate praseodymium nitrate mixed aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(9) described urge is produced within 4 hours in 550 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Embodiment 7】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 5.1 grams of concentration be 20w% (with Al2O3Meter)
Aluminum sulfate aqueous solution, 48 grams of MWW zeolite seed crystals, 20 grams of dimethyl dipropyl ammonium bromide mix with 30 grams of water, and are with concentration
PH is transferred to 10 by the 10w% NaOH aqueous solution, continues stirring 30 minutes, is moved into stainless steel cauldron, small in 150 DEG C of crystallization 72
When, filtering, washing, the XRD powder diffraction spectrums of dried product exhibited also have one more to change peak, table as accompanying drawing 1 at 7 °~11 °
Product prepared by the bright present invention is the Hydrogen stratiform MWW zeolite precursors 1 of unordered accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 5w%,
50 DEG C of ion exchanges obtain ammonium type MWW zeolites for 8 hours；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 3 hours through 600 DEG C of roastings；
(5) weigh 60 grams of Hydrogen MWW zeolite powders to mix with 6.7 grams of alumina powders, by 100:50 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) weigh 49.85 grams of catalyst carriers with 50 grams containing Pt0.13 grams, containing La0.0165 grams, containing Pr0.0035 grams
Chloroplatinic acid lanthanum nitrate praseodymium nitrate mixed aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 3 hours in 600 DEG C of roastings；
(9) described urge is produced within 8 hours in 300 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Comparative example 1】
1st, catalyst preparation：
(1) by 300 grams of concentration be 40w% (with SiO2Meter) Ludox, 17 grams of concentration be 20w% (with Al2O3Meter) sulphur
Sour aluminum water solution, 20 grams of dimethyl diethyl ammonium bromide mix with 30 grams of water, and with the NaOH aqueous solution that concentration is 10w% by pH
10 are transferred to, continues stirring 30 minutes, is moved into stainless steel cauldron, in 150 DEG C of crystallization 72 hours, filtering, washing, is produced after drying
The XRD powder diffraction spectrums of thing also have one more to change peak as accompanying drawing 1 at 7 °~11 °, show that product prepared by the present invention is nothing
The Hydrogen stratiform MWW zeolite precursors 1 of sequence accumulation；
(2) above-mentioned Hydrogen MWW zeolite precursors 1 are obtained into Hydrogen MWW zeolite precursors 2 in 3 hours through 550 DEG C of roastings；
(3) by 80 grams of above-mentioned Hydrogen MWW zeolite precursors 2 through being mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 10w%,
Ammonium type MWW zeolites are obtained within 3 hours in 60 DEG C of ion exchanges；
(4) ammonium type MWW zeolites obtain Hydrogen MWW zeolites in 3 hours through 550 DEG C of roastings；
(5) weigh 60 grams of Hydrogen MWW zeolite powders to mix with 25.7 grams of alumina powders, by 100:60 solid-liquid weight ratio
The aqueous solution of nitric acid that concentration is 0.5w% is added, is mediated, extrusion forming obtains precursor carrier；
(6) precursor carrier is dried 6 hours in 110 DEG C, then catalyst carrier is obtained within 3 hours through 550 DEG C of roastings；
(7) weigh 49.85 grams of catalyst carriers to mix containing Pt0.15 grams of chloroplatinic acid aqueous solution with 50 grams, 120 DEG C of dryings 5
Hour obtains catalyst precarsor I；
(8) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(9) described urge is produced within 6 hours in 450 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
【Comparative example 2】
(1) 160 grams of SiO/ with MWW structures are taken2/Al2O3Mol ratio be 60 non-layered Hydrogen MCM-22 zeolites with
Aluminum oxide presses 70 by weight：30 mixing, by 100:60 solid-liquid weight is pinched than adding the aqueous solution of nitric acid that concentration is 0.5w%
Conjunction, extrusion forming, drying.After being calcined 6 hours at 500 DEG C in atmosphere, carrier is produced；
(2) weigh 49.85 grams of catalyst carriers with 50 grams containing Pt0.13 grams, containing La0.013 grams, containing Pr0.007 grams of chlorine
Platinic acid lanthanum nitrate praseodymium nitrate mixed aqueous solution mixes, and 120 DEG C of dryings obtain catalyst precarsor I in 5 hours；
(3) the catalyst precarsor I is obtained into catalyst precarsor II in 4 hours in 450 DEG C of roastings；
(4) described urge is produced within 6 hours in 450 DEG C of reduction in the hydrogen nitrogen mixture atmosphere of hydrogen 5% (volume ratio)
Agent.
Carrier and catalyst preparation conditions are shown in Table 1, table 2, table 3.
2nd, evaluating catalyst
Evaluation is carried out in fixed bed reactors, and reaction temperature is 360 DEG C；Reaction pressure is 1.0MPa；C8Aroamtic hydrocarbon raw material
Weight space velocity be 8 hours-1, hydrogen and C8The mol ratio of aroamtic hydrocarbon raw material is 3.5.By weight percentage, C8The group of aroamtic hydrocarbon raw material
Turn into：Meta-xylene 60%, paraxylene 3%, ortho-xylene 32%, ethylbenzene 5%
Evaluation result is to be shown in Table 4.
Table 1
* MCM-22, non-laminar MWW zeolites
Table 2
* MCM-22, non-laminar MWW zeolites
Table 3
Table 4
Claims (9)
1. zeolite type alkyl aromatic hydrocarbon isomerization catalyst is layered, by weight percentage including following components：
A) 30~90%SiO2/Al2O3Mole be 5~200 the layering zeolite with MWW structures；
B) 0.05~1%Pt；
C) 0.001~0.1% lanthanide series；
D) surplus is aluminum oxide.
2. the preparation method of the layering zeolite type alkyl aromatic hydrocarbon isomerization catalyst described in claim 1, comprises the following steps：
(1) mixture containing silicon source, silicon source, template, alkali metal ion and water that pH first is 7.5~14 is at 80~200 DEG C
Crystallization obtains precursor carrier in 5~400 hours；
The mixture is formed with molar ratio computing is：Alkali metal ion/SiO2=0.01~4；Template/SiO2=0.01~4；
The template has below general formula：
Wherein R1For-(CH2)mCH3；R2For-(CH2)nCH3；R3For-(CH2)lCH3；R4For-(CH2)kCH3；
M, n and l are 0~3 integer, and m >=n, and m>l,m>k；Y is selected from halogen or OH；Alkali metal is derived from Li, Na, K, Ru, Cs
At least one of；
(2) aluminum oxide is binding agent, and shaping obtains precursor carrier 2；
(3) roasting obtains carrier；
(4) carrier is mixed with the soluble compound solution of Pt and lanthanide series, obtains catalyst precarsor I；
(5) reducing catalyst precursor I obtains described catalyst；
It is crystal seed that the mixture of step (1), which also contains with MWW structures layered zeolite, and it accounts for the mixing by weight percentage
SiO in thing2The 0.02~40% of weight.
3. preparation method according to claim 2, it is characterised in that silicon source be selected from silester, amorphous silica,
At least one of Ludox, silica gel, diatomite or waterglass；Silicon source is selected from aluminium hydroxide, aluminium isopropoxide, aluminium secondary butylate, aluminium
At least one of sour sodium, aluminum sulfate, aluminum nitrate, aluminium chloride, aluminum oxide.
4. preparation method according to claim 2, it is characterised in that have MWW structural stratification zeolites silica alumina ratio be
20~100.
5. preparation method according to claim 2, it is characterised in that step (5) uses hydrogen reducing.
6.C8The isomerization method of aromatic hydrocarbons, in the presence of the catalyst described in claim 1, with C8Aromatic hydrocarbons is that isomery occurs for raw material
Change reaction and obtain isomerization product.
7. isomerization method according to claim 6, it is characterized in that reaction temperature is 250~600 DEG C.
8. isomerization method according to claim 6, it is characterized in that pressure is calculated as 0.06MPa~10MPa with gauge pressure.
9. isomerization method according to claim 6, it is characterized in that the weight space velocity of the raw material is 0.6~210 small
When-1。
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| CN1989089A (en) * | 2004-07-29 | 2007-06-27 | 埃克森美孚化学专利公司 | Xylenes isomerization catalyst system and use thereof |
| CN101306382A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Catalyst for alkyl aromatics isomerization |
| CN102441419A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | C8Aromatic hydrocarbon isomerization catalyst and preparation method and application thereof |
| CN102452665A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Process for preparing layered zeolite having MWW structure |
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| DE69907935T2 (en) * | 1998-09-22 | 2004-03-11 | Exxonmobil Chemical Patents Inc., Baytown | METHOD FOR THE PRODUCTION OF ZEOLITHS WITH A HIGH SIO2 CONTENT BONDED BY ZEOLITH AND THEIR USE |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1989089A (en) * | 2004-07-29 | 2007-06-27 | 埃克森美孚化学专利公司 | Xylenes isomerization catalyst system and use thereof |
| CN101306382A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Catalyst for alkyl aromatics isomerization |
| CN102441419A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | C8Aromatic hydrocarbon isomerization catalyst and preparation method and application thereof |
| CN102452665A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Process for preparing layered zeolite having MWW structure |
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